CN111788168B - Process for manufacturing a silicon carbide coated body - Google Patents
Process for manufacturing a silicon carbide coated body Download PDFInfo
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- CN111788168B CN111788168B CN201880090409.3A CN201880090409A CN111788168B CN 111788168 B CN111788168 B CN 111788168B CN 201880090409 A CN201880090409 A CN 201880090409A CN 111788168 B CN111788168 B CN 111788168B
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- sic
- graphite substrate
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 588
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 569
- 238000000034 method Methods 0.000 title claims abstract description 377
- 230000008569 process Effects 0.000 title claims abstract description 315
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 517
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 456
- 239000010439 graphite Substances 0.000 claims abstract description 456
- 239000000758 substrate Substances 0.000 claims abstract description 420
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 190
- 239000011148 porous material Substances 0.000 claims description 243
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 239000012535 impurity Substances 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 44
- 239000001301 oxygen Substances 0.000 claims description 43
- 229910052760 oxygen Inorganic materials 0.000 claims description 43
- 238000010926 purge Methods 0.000 claims description 43
- 239000000460 chlorine Substances 0.000 claims description 36
- 229910052801 chlorine Inorganic materials 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims 1
- 229910021419 crystalline silicon Inorganic materials 0.000 claims 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 abstract description 209
- 239000000463 material Substances 0.000 abstract description 116
- 238000000151 deposition Methods 0.000 abstract description 67
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 15
- 229910000077 silane Inorganic materials 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 235000012431 wafers Nutrition 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 description 119
- 239000011248 coating agent Substances 0.000 description 105
- 230000015572 biosynthetic process Effects 0.000 description 95
- 239000010410 layer Substances 0.000 description 90
- 239000002243 precursor Substances 0.000 description 76
- 230000001976 improved effect Effects 0.000 description 74
- 239000013078 crystal Substances 0.000 description 63
- 230000008021 deposition Effects 0.000 description 35
- 239000007789 gas Substances 0.000 description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 32
- 238000001994 activation Methods 0.000 description 26
- 239000011572 manganese Substances 0.000 description 25
- 239000002245 particle Substances 0.000 description 22
- 238000011049 filling Methods 0.000 description 21
- 229910052748 manganese Inorganic materials 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 20
- 238000005660 chlorination reaction Methods 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 238000011282 treatment Methods 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 17
- 230000012010 growth Effects 0.000 description 17
- 238000000746 purification Methods 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- -1 hafnium nitride Chemical class 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007770 graphite material Substances 0.000 description 9
- 230000003698 anagen phase Effects 0.000 description 8
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000002513 implantation Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000005055 methyl trichlorosilane Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000005048 methyldichlorosilane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- DMEXFOUCEOWRGD-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(Cl)O[Si](C)(C)Cl DMEXFOUCEOWRGD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical group Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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Abstract
The present invention relates to a new process for manufacturing a SiC coated body by depositing silicon carbide (SiC) on a graphite substrate using Dimethyldichlorosilane (DMS) as a silane source in a chemical vapour deposition process. Another aspect of the invention relates to a new silicon carbide coated body obtainable by the new process of the invention and to the use of said silicon carbide coated body for the manufacture of articles for high temperature applications, susceptors and reactors, semiconductor materials and wafers.
Description
Technical Field
The present invention relates to a new process for manufacturing a SiC coated body by depositing silicon carbide (SiC) on a graphite substrate using Dimethyldichlorosilane (DMS) as a silane source in a chemical vapour deposition method. Another aspect of the invention relates to a new silicon carbide coated body obtainable by the new process of the invention and to the use of said silicon carbide coated body for the manufacture of articles for high temperature applications, susceptors and reactors, semiconductor materials and wafers.
Background
SiC-coated bodies are important products in various technical fields and are particularly useful for high temperature applications such as susceptors and wafers for applied materials and reactors, semiconductor materials, chip manufacturing, etc.
In particular, in high temperature applications and when applied in high precision devices, it is particularly important to provide SiC coated bodies (SiC coated articles) that exhibit excellent mechanical properties, such as intimate attachment (adhesion) of the SiC coating to the underlying substrate. In addition, we are particularly concerned with the high etch resistance, impact resistance, fracture toughness and/or crack resistance of SiC-coated bodies. In order to provide oxidation resistance of the coated body, it is further required that the SiC coating is applied uniformly and continuously, thereby providing an impermeable coating on the coated substrate surface.
The inventors of the present invention have surprisingly found that by the novel process as described herein, SiC can be deposited not only as a layer coating the surface of the underlying graphite substrate, but also to achieve the formation of SiC tendrils grown into the pores of the porous graphite substrate formed from the improved deposited SiC material. This provides improved physical and mechanical properties to the SiC-coated graphite article. In particular, the formation of tendrils formed from the improved SiC material and extending into the porous graphite provides significantly improved mechanical properties, as described in more detail below.
There are different methods for applying SiC coatings to various substrates by Chemical Vapor Deposition (CVD), including methods that use DMS as a silane source (also known as a CVD precursor) in CVD processes and deposition of SiC onto carbon-containing substrates, including graphite.
GB 1,128,757 describes a process for the preparation of SiC and describes a CVD process using a mixture of hydrogen and a carbon-containing compound and a silicon-containing compound or a mixture of hydrogen and a compound containing both carbon and silicon to form silicon carbide which crystallizes as a dense, substantially impermeable film of predominantly β -silicon carbide on a heated surface. In particular, the method is controlled to form stoichiometric silicon carbide. This document mentions DMS in particular as a compound containing both carbon and silicon, but does not provide for controlling the specific process conditions under which stoichiometric SiC is formed from DMS. Nor is the formation of whiskers described, let alone the specific process conditions that enable the formation of SiC whiskers that extend into the coated substrate.
Similarly, JP2000-302576 describes a method for preparing SiC-coated graphite materials using a CVD method and mentions, inter alia, DMS as a possible CVD precursor. However, of these, SiC is deposited only on the surface of the graphite substrate, and Si-containing gas infiltrated porous graphite substrates are discussed as being disadvantageous due to the difficulty of forming a uniform layer and the additional cost for additional coating of the infiltrated intermediate layer. Neither is there any teaching disclosed about the specific process conditions for using DMS as a CVD precursor, nor is there any teaching found about the possible formation of whiskers extending into the coated substrate.
Both EP 0935013 a1 and EP 1072570 a1 describe methods of depositing a SiC coating on a graphite substrate and thereafter removing the substrate. Thus, none of the documents teach the formation of SiC tendrils extending into the porous graphite to form a tightly connected SiC coating. In addition, none of the documents describes specific process conditions for achieving the effects of the present invention. In particular, EP 0935013 teaches relatively high temperature conditions for CVD processes. Although both documents generally mention the possibility of using DMS as a CVD precursor, neither of the documents teaches suitable process conditions for depositing substantially stoichiometric SiC (i.e., SiC having a Si: C ratio of 1: 1) by using DMS.
US 9,371,582 teaches a method of depositing SiC using Microwave Plasma Enhanced Chemical Vapour Deposition (MPECVD). The very specific plasma-based process described differs significantly from the process conditions described in the present invention and, therefore, no conclusion can be drawn that similar effects as have been found within the present invention can be achieved thereby.
EP 0294047 a1 relates to a process for minimizing the carbon content in semiconductor materials by pretreating carbon-containing surfaces used for the preparation of the semiconductor materials, and mentions the general possibility of coating graphite samples with SiC using CVD and, for example, using DMS as a CVD precursor. The specific process conditions to achieve the formation of SiC tendrils extending into the coated substrate are not described.
EP 0121797 a2 describes the preparation of carbon-silicon composite articles comprising the deposition of an impermeable, uniform SiC coating by CVD on a starting substrate. Example 6 mentions the use of DMS as a CVD precursor to wrap the substrate fiber with a film. Example 9 mentions the deposition of a SiC coating by CVD using methylchlorosilanes in and on the molded granular graphite as substrate to form an intermediate substrate. No specific process conditions are described to achieve the formation of SiC tendrils extending into the coated porous graphite substrate.
US 4,976,899 a describes the deposition of SiC in the presence of methane and hydrogen by the well-known Chemical Vapour Deposition (CVD) method using, for example, DMS, onto a porous composite matrix comprising reinforcing carbon fibres coated with carbon and SiC, the reinforcing carbon fibres being embedded in a deformable resin and a carbon-based matrix. Wherein the composite matrix is covered by a SiC coating that can penetrate and wet the porous structure of the resin substrate. The SiC coating applied therein exhibits cracking that must be subsequently filled and sealed by applying another overcoat (e.g., an aluminum nitride or hafnium nitride coating) and another outer alumina coating or borosilicate glass to provide a coated article sufficient to achieve the required thermal and oxidation protection. Specific process conditions to achieve the formation of SiC tendrils extending into the uniformly coated porous graphite substrate are not described.
US 3,925,577 a describes a process for producing a coated isotropic graphite member which comprises depositing a layer of silicon on a porous graphite body by gas phase reaction at a temperature below the melting point of silicon, followed by heating the graphite member with the applied layer of silicon to a temperature such that the silicon melts and penetrates into the pores of the graphite and causes the silicon to react in situ with the graphite to form a layer of silicon carbide, and further depositing a sealing layer of silicon carbide by gas phase reaction over the underlying previously reacted layer of silicon carbide. The graphite used therein is defined to exhibit a porosity equal to about 18 to 25% of the volume of the component, which is particularly described as mandatory to provide isotropic fine-grained graphite coated with silicon carbide having the desired strength properties. Deviations from the defined graphite properties are said to cause the composite to exhibit detached, cracked or disintegrated coatings in high temperature applications. The process described therein includes a forced step of surface cleaning the heat treated isotropic graphite member prior to subjecting the graphite article to the SiC coating step, thereby removing any loose surface particles. The CVD process described therein is carried out using silicon tetrachloride as the CVD precursor in the presence of hydrogen and methane. Argon may also be present as an inert gas. The use of DMS as a CVD precursor or silane source is not mentioned. No specific process conditions are described for achieving the improved SiC coated article of the present invention in which SiC tendrils extending into the coated porous graphite substrate are formed.
US2012/040139 and corresponding US 9,145,339 describe a very similar process for depositing SiC by allowing molten silicon to penetrate into a porous substrate material. The substrate is described as having a porosity of 25% to 45%. Allowing molten silicon to penetrate into the porous substrate requires the presence of large pores, which is reflected in high porosity, similar to US 3,925,577 a discussed above. However, the large pores and high porosity are detrimental to the mechanical properties and strength of the graphite substrate. In addition, by using molten silicon, high crystallinity SiC cannot be obtained but only amorphous SiC can be obtained, as can be seen from fig. 9 below.
In addition, US2018/002236 (and JP2002-003285, which is cited here as prior art document 1) relates to a process for depositing SiC on a porous substrate having a relatively high porosity of 12% to 20% and preferably a porosity of at least 15%. It is noted that SiC cannot be deposited in the depth of the substrate by the CVD method unless the porosity is 15% to 50%. In both documents, only DMS is mentioned broadly as a CVD precursor. Both documents describe specific process conditions only for different CVD precursor materials, such as in the example of US2018/002236, deposition of SiC on a substrate with 16% porosity using Methyltrichlorosilane (MTS). In the cited example of JP2002-003285, the CVD precursor is also methyltrichlorosilane without specifying a particular porosity. The improved crystalline SiC material according to the present invention cannot be deposited in graphite substrates having lower porosity with the process described therein. No tendrils according to the present invention can be formed with the process described therein.
US 3,406,044 a describes a process for making a heating resistant element comprising applying silicon to a carbonaceous material by chemical vapour deposition using trichlorosilane. With the process applied therein, a silicon layer is applied to the substrate, which silicon layer penetrates into the porous substrate and is converted therein to a certain amount of SiC. With the process described therein, a silicon layer is applied which contains about 9% of an amount of SiC but a relatively small amount. It is further described therein that the applied SiC coating does not penetrate the pores of the graphite substrate substantially, but forms a rather gas-tight impermeable coating on the surface of the graphite. The use of DMS as a CVD precursor is not mentioned. No specific process conditions are described for achieving the improved SiC coated article of the present invention in which SiC tendrils extending into the coated porous graphite substrate are formed.
US 3,622,369 describes a process for depositing stoichiometric silicon carbide on a resistively heated wire using methyldichlorosilane and hydrogen along with a carbonization gas such as methane in a CVD process. It is described that by using the specific mixture of methyldichlorosilane with hydrogen and methane as the silane source, silicon carbide filaments are formed. However, it is neither described that such SiC filaments can be grown into porous graphite substrates, nor that such filaments can be formed under different CVD reaction conditions (such as with other CVC precursor materials such as DMS in the presence of hydrogen gas without the addition of methane gas). In particular, the process conditions for achieving the improved SiC coated article of the present invention, in which SiC tendrils extending into the coated porous graphite substrate are formed, are not described.
GB 1,021,662 describes a method of filling the pores of a porous substrate by chemical vapour deposition of an organosilicon compound by treating the porous body with the aim of reducing the porosity and permeability of the porous body. The porous bodies described therein relate primarily to silicon carbide bodies, but graphite, alumina and other porous inorganic bodies are also mentioned. In which the holesThe reduction in porosity is carried out by depositing SiC in the pores of the porous body using chemical vapor deposition of an organosilicon compound. Preferred organosilicon compounds are used which provide a SiC to C ratio of 1: 1. Since dimethyldichlorosilane by itself is not suitable for providing such a 1:1 ratio, only such organosilicon compounds are mentioned as compounds which react with the silicon-generating compounds (such as SiCl) 4 ) Combined with possible CVD precursors. In addition, only one specific example describes the deposition of SiC on a carbon substrate, i.e., example 3, by the presence of CH 3 SiCl 3 CVD was performed to deposit SiC on a piece of artificial graphite with 18% porosity. According to said example 3, the porosity can be reduced to 15%, which indicates that only a low degree of pore filling can be achieved. No specific process conditions are described for achieving the improved SiC coated article of the present invention in which SiC tendrils extending into the coated porous graphite substrate are formed.
Cagliiostro and S.Ricciitiello (J.am.Ceram.Soc.,73(3) 607-14; 1990) describe the analysis of the pyrolysis products of Dimethyldichlorosilane (DMS) in a CVD process using argon as the purge gas. The publication teaches that the volatility, transport properties and reaction kinetics of the components formed in the CVD process affect the ability to penetrate, condense and/or coat the porous media and thus affect morphology, densification and/or mechanical properties. This clearly supports the finding of the present invention that very specific process conditions are critical to achieving the surprising effects described herein. For example, it has been found that the particular choice of CVD precursors, purge gases, CVD conditions (such as temperature, pressure, and deposition time) can significantly affect the results in a CVD process.
This was confirmed by Byung Jin Choi (Journal of Materials Science Letters 16, 33-36; 1997). Among them, variations in the structure of SiC deposited in a CVD method using different CVD precursors and applying varying CVD conditions (e.g., different temperatures) have been studied. In particular, DMS has been used as a CVD precursor at different temperatures, and stoichiometric SiC formation has been observed. However, it can be seen that under the applied CVD conditions, only amorphous SiC is deposited, as shown therein (fig. 7a), and that varying the temperature can significantly affect the formation of SiC and by-products, as can be seen in the XRD pattern (fig. 3). In addition, the publication does not describe deposition of SiC on a porous substrate and thus does not describe formation of SiC tendrils extending into the porous substrate.
Disclosure of Invention
Object of the Invention
It is an object of the present invention to provide a new process which allows the preparation of articles comprising SiC-coated graphite substrates, which avoids the drawbacks of the prior art processes.
It is another object of the present invention to provide a process that can provide a SiC coated article in which the SiC coating forms a tightly connected layer on the underlying graphite substrate.
It is another object of the invention to provide a process that avoids the formation of cracks and fractures in the SiC coating.
It is another object of the present invention to provide a process for preparing SiC-coated graphite substrate articles in a cost and time efficient manner by minimizing the number of required process steps.
Another object of the present invention is to provide a process for preparing graphite-substrate-based articles with SiC coating, which on the one hand exhibit sufficient mechanical resistance and strength and on the other hand also have maximum continuity and uniformity, so that it is no longer necessary to apply additional coatings or sealing layers, for example to seal the cracks that occur.
It is another object of the present invention to provide a new and improved SiC-coated graphite substrate body having the desired improved properties as described herein.
It is a particular object of the present invention to provide a new and improved SiC-coated graphite substrate body having excellent mechanical strength, with SiC deposited thereon having improved properties and characteristics, and comprising a SiC coating forming a layer in intimate connection with the underlying graphite substrate. It is another object of the present invention to provide a new and improved SiC-coated graphite substrate body having improved SiC characteristics with respect to SiC deposition and infiltration, SiC crystallinity, density, purity, Si: C ratio and/or strength.
It is another object of the present invention to provide a new and improved SiC-coated graphite substrate body having improved graphitic properties with respect to grain size, density and/or porosity.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having a substantially pure SiC coating.
It is another object of the present invention to provide an improved SiC coated graphite substrate body having an improved SiC material deposited thereon and/or therein.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having an improved SiC material with high crystallinity and/or high tetrahedral crystallinity and/or containing a small amount of amorphous SiC.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having a significantly lower content of free Si in the SiC coating.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having an improved average coefficient of thermal expansion between the graphite substrate and the SiC coating.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having improved residual compressive loading in the SiC layer.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having improved impact resistance.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having improved fracture toughness.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having improved exfoliation, peel and/or warp resistance.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having improved adhesion between the graphite substrate and the SiC coating.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having an improved relationship between the dimensions of the outer (upper) surface of the SiC coating and the dimensions of the interfacial layer formed by SiC tendrils extending into the porous graphite substrate.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having a multi-layer SiC coating.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body having such a multi-layer SiC coating, wherein at least two SiC layers of different porosity and/or density are present.
It is another object of the present invention to provide an improved SiC-coated graphite substrate body as described herein, which further has such a multilayer SiC coating.
It is another object of the present invention to provide a new process for preparing such an improved SiC-coated graphite substrate body.
It is another object of the invention to provide a new method for depositing stoichiometric SiC on a substrate in a CVD process.
It is another object of the invention to provide a new method for depositing stoichiometric SiC on a substrate in a CVD process without adding methane gas.
It is another object of the present invention to provide an improved graphite substrate, in particular for use and applications as described herein.
It is another object of the present invention to provide such an improved graphite substrate having improved purity.
It is another object of the present invention to provide such an improved graphite substrate having a modified surface porosity.
It is another object of this invention to provide such an improved graphite substrate having pores with enlarged surface pore sizes.
It is another object of the present invention to provide such an improved graphite substrate having a specified chlorine content.
It is another object of the present invention to provide a new process for preparing such an improved graphite substrate.
It is another object of the present invention to provide an activated graphite substrate having a modified surface porosity, in particular for use and application as described herein.
It is another object of the present invention to provide such an activated graphite substrate having improved purity.
It is another object of the present invention to provide such an activated graphite substrate having a specific chlorine content.
It is another object of the present invention to provide a novel method for preparing such activated graphite substrates.
Another object of the invention is to provide a new method for depositing SiC on a substrate in a CVD process without using argon as purge gas.
The inventors of the present invention have surprisingly found that these objects can be solved by a novel process according to the present invention, which is described in detail below.
Preferred embodiments of the invention
The independent claims describe embodiments of the invention for solving at least one of the above mentioned objects of the invention. The dependent claims provide further preferred embodiments contributing to solving at least one of the above mentioned objects of the invention.
[1] A process for manufacturing an activated graphite substrate having a modified surface porosity, comprising the steps of i) positioning a graphite substrate in a process chamber, the graphite substrate having an open porosity and comprising pores having an average pore size (pore diameter) in the range of 0.4 μ ι η to 5.0 μ ι η and comprising pores having a surface pore diameter < 10 μ ι η and having an average grain size < 0.05 mm;
ii) purging the graphite substrate with nitrogen in the process chamber until the oxygen content in the process chamber is about 5.0%;
iii) heating the porous graphite substrate in a furnace to a temperature of at least about 1000 ℃;
iv) continuing to purge the porous graphite substrate with nitrogen and heating the porous graphite substrate to a temperature of > 1000 ℃ until the oxygen content is < 0.5%.
[2] The process according to embodiment [1], further comprising a step v) following step iv): the porous graphite substrate is annealed to reduce stress in the porous graphite substrate by maintaining the porous graphite substrate at a temperature > 1000 ℃.
[3] The process according to embodiment [1] or [2], comprising the further step vi): the porous graphite substrate is directly subjected to a chemical vapor deposition process, preferably without a prior cleaning step.
[4] The process according to any one of the preceding embodiments, wherein in step ii) the nitrogen is purged until the oxygen content in the process chamber is about 3.0%, preferably about 2.5%.
[5] The process according to any one of the preceding embodiments, wherein in step iv) the heating is continued until the oxygen content is reduced to ≦ 0.3%, preferably ≦ 0.2%, preferably ≦ 0.1%.
[6] The process according to any one of the preceding embodiments, wherein the graphite substrate of step i) exhibits a chlorine content of at least about 20.00ppb wt., preferably at least about 40.00ppb wt., preferably at least about 60.00ppb wt.
[7] The process according to embodiment [6], wherein chlorine is present in the graphite substrate at ≧ 50 μm below the main surface.
[8] The process according to any one of the preceding embodiments, wherein the temperature in steps iii) and iv) is between > 1000 ℃ and 1500 ℃, preferably between 1000 ℃ and 1200 ℃.
[9] The process according to any one of the preceding embodiments, wherein the process is controlled to obtain a graphite substrate with modified porosity comprising pores with an enlarged average pore size (pore diameter) compared to the graphite substrate used in step i).
[10] The process according to any one of the preceding embodiments, wherein the process is controlled to obtain a graphite substrate having a modified porosity comprising pores having an average pore size (pore diameter) enlarged by a factor of 1.2 to 2.0 compared to the graphite substrate used in step i).
[11] The process according to any one of the preceding embodiments, wherein the process is controlled to obtain a graphite substrate with modified porosity comprising pores with a surface pore size of ≧ 10 μm, preferably ≧ 10 μm up to 30 μm.
[12] The process according to any one of the preceding embodiments, wherein the process is controlled to obtain a graphitic substrate with modified porosity comprising pores with an expanded surface pore size that is expanded by a factor of 2.0, preferably by a factor of 3.0, preferably by a factor of 4.0, preferably by a factor of 5.0, preferably by a factor of 6.0, preferably by a factor of 7.0, preferably by a factor of 8.0, preferably by a factor of 9.0, preferably by a factor of 10.0 compared to the graphitic substrate used in step i).
[13] The process according to any one of the preceding embodiments, wherein the graphite substrate has an average grain size of ≦ 0.04mm, preferably ≦ 0.03mm, preferably ≦ 0.028mm, preferably ≦ 0,025mm, preferably ≦ 0.02mm, preferably ≦ 0,018mm, preferably ≦ 0.015 mm.
[14]The process according to any one of the preceding embodiments, wherein the graphite substrate has ≧ 1.50g/cm 3 Preferably ≥ 1.70g/cm 3 Preferably ≥ 1.75g/cm 3 The density of (2).
[15] The process according to any one of the preceding embodiments, wherein the porous graphite substrate comprises an amount of one or more of the following impurity elements
Calcium < 50.00ppb by weight,
magnesium < 50.00ppb by weight,
aluminum < 50.00ppb by weight,
titanium < 10.00ppb by weight,
chromium is less than 100.00ppb by weight,
manganese < 10.00ppb by weight,
copper < 50.00ppb wt. -%,
iron < 10.00ppb wt. -%,
cobalt < 10.00ppb by weight,
nickel < 10.00ppb by weight,
zinc < 50.00ppb by weight,
molybdenum < 150.00ppb wt.
[16] The process according to any one of the preceding embodiments, wherein the porous graphite substrate has a purity of 98% or more, preferably 99% or more.
[17] The process according to any one of the preceding embodiments, wherein the porous graphite substrate has a total amount of impurities of 10.00ppm wt. -%, preferably 5.00ppm wt. -%, preferably 4.00ppm wt. -%, preferably 3.50ppm wt. -%.
[18] An activated graphite substrate having modified surface porosity obtainable by a process according to any one of the preceding embodiments.
[19] An activated graphite substrate having a modified surface porosity, the activated graphite substrate having a chlorine content as defined in embodiment [6] and/or [7 ].
[20] The activated graphite substrate with modified surface porosity according to embodiments [18] and [19], comprising pores with enlarged average pore size (pore diameter) and comprising pores with surface pore diameter ≥ 10 μm, preferably ≥ 10 μm up to 30 μm.
[21] The activated graphite substrate with modified surface porosity according to embodiments [18] to [20] has an average grain size < 0.05mm, preferably < 0.04mm, preferably < 0.03mm, preferably < 0.028mm, preferably < 0,025mm, preferably < 0.02mm, preferably < 0.018mm, preferably < 0.015 mm.
[22] The activated graphite substrate with modified surface porosity according to embodiments [18] to [21], has an open porosity with a porosity of 6% to 15%, preferably ≧ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
[23] The activated graphite substrate having modified surface porosity according to any one of embodiments [18] to [22], having a purity as defined in any one of embodiments [15] to [17 ].
[24] The activated graphite substrate with modified surface porosity according to any one of embodiments [18] to [23], further comprising a silicon carbide layer on one or more surfaces and/or on one or more selected and discrete surface regions.
[25] Use of the activated graphite substrate having modified surface porosity according to any one of embodiments [18] to [24] as a substrate in a silicon carbide coated graphite article.
[26] Use of an activated graphite substrate having modified surface porosity according to any one of embodiments [18] to [24] as a substrate in a Chemical Vapor Deposition (CVD) process for depositing silicon carbide on a substrate.
[27] Use of an activated graphite substrate having modified surface porosity according to any one of embodiments [18] to [24] as a substrate in a Chemical Vapor Deposition (CVD) process for depositing silicon carbide in pores of the activated substrate.
[28] According to the use of embodiments [26] and [27], dimethyldichlorosilane is used as a CVD precursor.
[29]According to embodiment [28]Use of (A) using H 2 As a purge gas.
[30] Use according to embodiment [29] for depositing silicon carbide in pores of an activated substrate to form a connected substantially tetrahedral crystalline SiC material in the form of tendrils extending in a length of at least 50 μ ι η.
[31] Use of an activated graphite substrate having a modified surface porosity obtainable by a process according to any one of embodiments [1] to [17] or as defined in any one of embodiments [18] to [24] for the manufacture of an article for high temperature applications, susceptors and reactors, semiconductor materials, wafers.
Detailed Description
I. Definition of
In the following description, a given range includes a lower threshold and an upper threshold. Thus, a definition in the sense of "in the range of X and Y" or "in the range between X and Y" for parameter a means that a can be any value of X, Y and any value between X and Y. The definition in the sense of "up to Y" or "at least X" of the parameter a accordingly means that a can be any value less than Y and Y, or a can be any value of X and greater than X, respectively.
According to the present invention, the term "about" in connection with a numerical value is meant to include deviations of ± 10%, preferably ± 8%, preferably ± 5%, preferably ± 3%, 2%, 1%.
The term "substantially" in connection with a described feature means that the feature is implemented at a significant level and/or predominantly in accordance with the invention, and is not limited to its complete and absolute implementation.
In the present invention, has the formula (CH) 3 ) 2 SiCl 2 The term "dimethyldichlorosilane" of (a) is usually abbreviated to DMS. DMS ((CH) 3 ) 2 SiCl 2 ) Also known as chlorodimethylsilane.
In the sense of the present invention, the term "tendril" or "tendrils" describes a deposited SiC material having a specific length and extending into the pores from the surface of the porous substrate, thereby providing a deep reaching anchor or hook-like firm connection between the outer SiC layer extending above the surface of the porous substrate and the porous substrate. In the sense of the present invention, tendrils take on a root-like or net-like morphology and appear to be elongated and branched, and may appear like tree roots, with nodular voids formed in the graphite. These tendrils are formed by growing substantially tetrahedral SiC crystals with a low content of amorphous SiC to a tightly connected crystalline SiC material extending in a length of at least 50 μm. This can be determined, for example, by SEM evaluation as shown in fig. 5a, 5b, 6a and 6b (whisker formation) and fig. 10 or by XRD pattern according to conventional method (substantially tetrahedral SiC crystal structure) as shown in fig. 11.
The term "crystallinity" or "crystal" referring to the crystallinity/crystal obtained in the process according to the invention generally means "beta-SiC" and/or "(substantially) tetrahedral crystals" as described herein.
The tetrahedral crystal structure is also shown below in fig. 10.
In the sense of the present invention, "porosity" generally refers to "open porosity" otherwise SiC tendrils will not be able to grow into the porous graphite substrate.
The Scanning Electron Microscope (SEM) measurements mentioned in the present invention as determination methods for example for determining porosity, pore modification, SiC particle size, interfacial layer thickness etc. preferably refer to SEM systems using Phenom ProX (5kV, 10kV and 15kV) at room temperature (about 24 ℃).
II. Process
A first aspect of the invention relates to a process for manufacturing a SiC coated body by depositing silicon carbide (SiC) on a graphite substrate using Dimethyldichlorosilane (DMS) as a silane source in a chemical vapour deposition process.
1. Process for preparing graphite substrate
One aspect of the process of the present invention relates to the preparation of graphite components for use as graphite substrates in said process.
The graphite substrate that will form the base or core of the SiC-coated element can be prepared from any suitable graphite element, for example, by cutting to the desired size and shape.
Preferably, graphite having a purity of at least 99% is used.
The graphite may then be subjected to further treatments, such as surface treatments (working of the graphite), in particular for applying specific surface structures. The surface structure may have a variable design and may be applied according to the needs and desires of the customer. The surface structure may be applied using conventional methods known in the art.
The graphite component thus pretreated forms what is known as a graphite preproduct.
According to the invention, it is particularly preferred to use a graphite substrate having an open porosity.
The graphite substrate preferably comprises small pores preferably having an average pore size (pore diameter) in the range of 0.4 μm to 5.0 μm. The graphite substrate having pores preferably includes pores having a surface pore size of < 10 μm. This means that a major or major amount of the pores exhibit a pore size or pore diameter < 10 μm. Exemplary embodiments of suitable graphite pre-products are shown in fig. 7a to 7 c.
It is further preferable to use a graphite substrate having a porosity of 6% or more and 15% or less. Preferably, the graphite used in the process of the present invention has a porosity of from about 6% to about 13%, preferably from about 11% to about 13%. Even more preferred is that the graphite substrate has an open porosity of 6% to 15%, preferably ≧ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
It is further preferable to use a graphite substrate of fine grain type, ultra-fine grain type and/or ultra-fine grain type. This graphite grain type indicates graphite having a particularly fine grain size. Preferably, the graphite substrate comprises an average grain size of < 0.05mm, more preferably the grain size is < 0.04mm, preferably < 0.03mm, preferably < 0.028mm, preferably < 0.025mm, preferably < 0.02mm, preferably < 0.018mm, preferably < 0.015 mm.
The graphite substrate preferably has ≥ 1.50g/cm 3 Preferably ≥ 1.70g/cm 3 Preferably ≥ 1.75g/cm 3 The density of (c).
The grain size, pore size/pore diameter and porosity may be determined using known methods, such as in particular by SEM (scanning electron microscope) measurements as indicated above.
Porosity factorIt is also possible to calculate the amount of pores per unit weight [ cm ] of the graphite substrate 3 /g]And bulk density [ g/cm ] 3 ]The product of (a). Thus, porosity can be expressed as [ volume/volume ] based on volume]。
The (bulk) density can be obtained by dividing the mass of the graphite sample by the volume of the sample.
The amount of pores per unit weight can further be measured under well known conditions using conventional equipment or with mercury intrusion methods as described, for example, in US2018/0002236 a 1.
The desired porosity and/or density may already be present in the graphite used to prepare the graphite pre-product. The desired characteristics may also be adjusted in the process steps of the present invention as described herein.
The properties defined above are advantageous with respect to the mechanical strength of the graphite substrate and the SiC-coated graphite body. As the porosity increases, the density of the substrate decreases, which weakens the substrate material and may cause cracking and defects or wear in high temperature applications or during high temperature CVD processes.
However, if the porosity and pore size are too small, it is difficult to introduce the silane source deep into the pores to form SiC tendrils therein. It is therefore another object of the present invention to find an appropriate balance between on the one hand good mechanical and physical strength and stability and the suitability for introducing SiC deep into the pores of the graphite substrate material used, and to determine appropriate process conditions that allow high quality SiC to be deposited deep within the pores of the graphite substrate without degrading the mechanical properties of the substrate to provide an improved SiC-coated article for high temperature applications.
2. Purification of graphite
Another process step involves another pretreatment of the graphite pre-product. Wherein the graphite pre-product is subjected to a purification and chlorination process. Thus, the individual elements of graphite pre-product are stacked in a furnace and purged with nitrogen while heating to about 2000 ℃. Chlorine gas was purged into the furnace to effect chlorination of the graphite pre-product. In principle, methods for purifying carbonaceous materials, such as graphite, by chlorination treatment to remove metallic element impurities are well known, for example from US2,914,328, WO 94/27909, EP 1522523 a1, EP1375423 or US 4,892,788. In known chlorination processes, argon is generally used as purge gas, the specific purpose of which is to reduce the nitrogen content in the graphite material. None of these documents describe the effect of the process conditions described therein on the porosity of the purified substrate.
However, the inventors of the present invention have found that in one particular aspect of the present invention, not only purified graphite components, but also graphite components having modified surface porosity can be prepared by applying very specific process conditions. Such a purified graphite component with modified surface porosity has proven to be particularly suitable for use as a graphite substrate in a CVD method according to the invention, since such a modified graphite component particularly contributes to the formation of SiC tendrils in the pores of the graphite substrate as described herein. In particular, the activated and modified surface porosity resulting from the purification and activation steps according to the invention proves to be surprisingly effective in maintaining the balance between graphite with small pores and low porosity to maintain the maximum mechanical strength of the substrate while having sufficient porosity to allow the silicon raw material to be introduced deep into the pores for SiC deposition and whisker formation within the graphite.
Accordingly, one aspect of the present invention relates to a process for manufacturing a purified graphite component having a modified surface porosity. The process comprises specific process steps
a) Providing a graphite member (e.g., the graphite pre-product mentioned above) having an open porosity and comprising pores having an average pore size (pore diameter) in the range of 0.4 μm to 5.0 μm and comprising pores having a surface pore diameter < 10 μm and having an average grain size < 0.05 mm;
b) purging the graphite component with nitrogen in the furnace until the oxygen content in the furnace is about 5.0%;
c) heating the porous graphite member in a furnace to a temperature of at least about 1000 ℃;
d) continuously purifying and heating the porous graphite component by using nitrogen until the oxygen content is less than or equal to 0.5 percent;
e) subjecting a porous graphite member directly to a chlorination treatment by
f) Increasing the temperature to > 1500 ℃ and starting to purge chlorine;
g) heating the porous graphite member to a temperature of 1700 ℃ or more in a chlorine atmosphere.
Surprisingly, it has been demonstrated that under this particular process condition, a purified graphite component having a modified surface porosity can be provided. Said surface porosity modification becomes evident in comparison with the surface porosity of the graphite component according to step a), i.e. before the treatment according to steps b) to g). The modification can be determined, for example, in a micrograph or by SEM (scanning electron microscope) measurements as indicated above and as shown in fig. 7a, 7b and 7c and in fig. 8a, 8b and 8c, fig. 7a, 7b and 7c showing the porosity of the graphite member before the treatment according to step a), i.e. according to steps b) to g), fig. 8a, 8b and 8c clearly showing the modified surface porosity of the graphite member after steps b) to g). With the described process, the surface porosity is modified, for example, by enlarging the surface pores to obtain a graphite substrate with modified porosity comprising pores with an enlarged average pore size (pore diameter) compared to the graphite substrate used in step a).
In particular, a graphite substrate with modified porosity may be obtained comprising pores with an enlarged average pore size (pore diameter) compared to the graphite substrate used in step a) and comprising pores with a surface pore diameter of ≧ 10 μm.
Preferably, a graphite substrate with modified porosity is obtainable comprising pores with an average pore size (pore diameter) enlarged by a factor of 1.2 to 2.0, preferably 1.2, preferably 1.3, preferably 1.5, preferably 2.0 compared to the graphite substrate used in step a).
Preferably, a graphite substrate with modified porosity is obtained comprising pores with a surface pore size of ≧ 10 μm, preferably ≧ 10 μm to 30 μm.
Preferably, a graphite substrate with modified porosity is obtainable comprising pores with an enlarged surface pore size enlarged by a factor of 2.0, preferably a factor of 3.0, preferably a factor of 4.0, preferably a factor of 5.0, preferably a factor of 6.0, preferably a factor of 7.0, preferably a factor of 8.0, preferably a factor of 9.0, preferably a factor of 10.0 compared to the graphite substrate used in step a).
Preferably, the modification causes the surface pore size of the graphite pores to be enlarged, which means that the inlets to the pores are expanded and thus provide an inlet or funnel or cone which supports the introduction of the Si gas deep into the pores of the porous graphite member. This has the advantage that the inlet for Si gas is large, while the total porosity of the graphite is still small to maintain the mechanical stability and strength of the material.
Thus, an enlarged surface pore size according to the present invention may also mean an enlargement at the surface of the substrate relative to the diameter of the pores within the substrate.
Thus, the process steps b) to d) are controlled to achieve the surface porosity modification described above.
In particular, such surface porosity modification comprises enlarging the opening diameter in the graphite surface compared to the opening diameter of the graphite member according to step a). Under this particular process condition, the average opening diameter in the graphite surface may increase by at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%, preferably at least 55%, preferably at least 60%. In particular, the average pore diameter in the graphite surface may increase by more than 60%, such as for example 60% to 100%. This surface porosity modification provides a modified surface structure that promotes and supports the formation of SiC tendrils that grow into and extend into the pores of the graphite member when used in a CVD process according to the invention.
In step b), the nitrogen is preferably purged until the oxygen content in the furnace is about 3.0%, preferably about 2.5%. If the oxygen content in step b) is higher than the content defined herein before heating the porous graphite member in step c), the graphite burns off and the pore structure is at least partially destroyed. If the oxygen content in step b) is below the content defined herein before heating the porous graphite member in step c), sufficient modification of the surface porosity cannot be achieved.
An oxygen/carbon monoxide meter Bacharach model 0024-7341 can be used to control the oxygen content.
Preferably, the temperature in steps c) and d) is between > 1000 ℃ and 1500 ℃, preferably between 1000 ℃ and 1200 ℃.
In step d), the purging with nitrogen and the heating are preferably continued until the oxygen content is reduced to ≦ 0.3%, preferably ≦ 0.2%, preferably ≦ 0.1%.
It is also possible to purge with nitrogen without starting to heat the graphite member until the desired low oxygen content is reached, and then to start heating the porous graphite member as defined above in step c).
Process steps b) to d) are carried out until the defined oxygen content has been achieved.
Without being bound by theory, it is believed that the purge gas nitrogen and oxygen residues present in the furnace react during combustion to form nitrogen oxides (NOx), which are well known for their reactivity, and thus are believed to further effect purification of the porous graphite member.
In one aspect of the particular process described herein, the graphite member that has been purified and optionally heated until the desired low oxygen content is reached is directly subjected to the chlorination process by starting heating the graphite member as defined in step f).
In step f) and/or g), the chlorine is preferably purged with 5 to 20, preferably 7 to 10slpm slpm (standard liters per minute) chlorine. The flow meter used to control the flow of chlorine gas may be that of a Sierra Instruments Digital MFC.
Preferably, the chlorination treatment of steps e) to g) is carried out for a period of time of about 1 to 4 hours, preferably 1 to 3 hours.
In step g), the temperature is raised to a value of 1700 ℃ or more. The temperature can also be raised to > 2000 ℃. Preferably, the chlorination treatment of steps e) to g) is carried out at a temperature not exceeding 2600 ℃, preferably the temperature in step g) is increased to > 1800 ℃ and < 2600 ℃, preferably to 1800 ℃ to 2500 ℃.
Preferably, the chlorination treatment is controlled to adjust the chlorine content in the porous graphite member to an amount of at least about 20.00ppb wt., preferably at least about 40.00ppb wt., preferably at least about 60.00ppb wt.
In another aspect, the chlorine content in the porous graphite member is adjusted to an amount of at least about 30.00ppb wt., preferably at least about 40.00ppb wt., preferably at least about 50.00ppb wt.
On the other hand, the chlorine content in the porous graphite member is adjusted to an amount in the range of about 20.00ppb wt. to 250.00ppb wt., preferably about 30.00ppb wt. to 250.00ppb wt., preferably about 40.00ppb wt. to 250.00ppb wt., preferably about 50.00ppb wt. to 250.00ppb wt.
On the other hand, the chlorine content in the porous graphite member is adjusted to an amount in the range of about 20.00ppb wt. to 250.00ppb wt., preferably about 20.00ppb wt. to 200.00ppb wt., preferably about 20.00ppb wt. to 175.00ppb wt., preferably about 20.00ppb wt. to 165.00ppb wt.
This chlorine content adjustment is particularly preferred in the above-described process with process steps e) to g).
Wherein the adjusted chlorine content as defined above is achieved in particular in deeper regions of the porous graphite member and not only in surface regions. Very particularly, with the chlorination treatment according to the present invention, the preferred chlorine content defined above can be achieved within the porous graphite member, particularly at a depth ≧ 50 μm below the major surface. The level of chlorination in the depth of the graphite member is preferred in order to achieve the desired degree of purity and introduction of chlorine into the graphite member.
The adjustment can be achieved in particular by the preferred chlorination conditions described above.
Without being bound by theory, it is believed that the introduction of chlorine into the graphite component provides a reservoir for the remaining chlorine that can enable further purification in the following process steps as described herein, for example in a CVD process as described herein. The particular porosity and/or density of the graphite member as defined herein is believed to be advantageous in order to introduce and retain residual chlorine in the graphite member. It is believed that this relatively dense graphite material supports the retention of chlorine in the graphite member.
According to the invention, a chlorination treatment is carried out to provide a purified porous graphite component, for example, the graphite component resulting from process step g) described above, which contains an amount of one or more of the following impurity elements
Calcium < 100.00ppb wt. -%,
magnesium < 100.00ppb by weight,
aluminum < 100.00ppb wt. -%,
titanium < 20.00ppb by weight,
chromium is < 200.00ppb wt. -%,
manganese < 20.00ppb by weight,
copper < 100.00ppb wt. -%,
iron < 20.00ppb wt. -%,
cobalt < 20.00ppb by weight,
nickel < 20.00ppb by weight,
zinc < 100.00ppb by weight,
molybdenum < 300.00ppb wt.;
preferably contains an amount of one or more of the following impurity elements
Calcium < 50.00ppb by weight,
magnesium < 50.00ppb by weight,
aluminum < 50.00ppb by weight,
titanium < 10.00ppb by weight,
chromium is less than 100.00ppb by weight,
manganese < 10.00ppb by weight,
copper < 50.00ppb wt. -%,
iron < 10.00ppb wt. -%,
cobalt < 10.00ppb by weight,
nickel < 10.00ppb by weight,
zinc < 50.00ppb by weight,
molybdenum < 150.00ppb wt.
According to the invention, the chlorination treatment is carried out to provide a porous member having a purity of 98% or more, preferably 99% or more.
The purification process according to the present invention preferably provides a porous graphite member having a total amount of impurities of 10.00ppm wt. or less, preferably 5.00ppm wt. or less, preferably 4.00ppm wt. or less.
The process of purification or purification and surface modification described above may further comprise the steps of: annealing the porous graphite member to maintain the porous graphite member at a temperature > 1000 ℃ to reduce stress in the porous graphite member.
The resulting purified porous graphite member may be subjected to surface cleaning to remove dust and loose particles from the surface of the treated graphite member.
In known graphite chlorination processes, the use of argon as a purge gas is quite common. The inventors of the present invention have surprisingly found that argon is not suitable as purge gas, in particular for preparing purified graphite components to be used in the CVD process described herein, in which CVD process tendencies are intended to form whiskers extending into the pores of the graphite. In contrast, the inventors found that if argon has been used as purge gas in the process of purifying graphite components, tendrils are not formed. In another aspect of the invention, it is therefore preferred to carry out the purification and chlorination processes in the absence of argon.
3. Activation of chlorided graphite
Another process step involves further pretreatment of the graphite pre-product or the purified and chlorinated graphite component described above. Wherein the graphite pre-product or the purified, chlorinated graphite component described above is subjected to an activation process. The inventors of the present invention have surprisingly found that in a further aspect of the present invention, the application of very specific process conditions is suitable for the preparation of activated graphite components having (further) modified surface porosity. Such activated graphite components with modified surface porosity prove to be particularly suitable for use as graphite substrates in the CVD process according to the invention, since such activated graphite components further contribute and support the formation of SiC tendrils extending into the pores of the graphite when used in the CVD process described below.
Accordingly, another aspect of the invention relates to a process for manufacturing an activated graphite substrate having a modified surface porosity. The process comprises specific process steps
i) Positioning a graphite substrate in the process chamber, the graphite substrate having an open porosity and comprising pores having an average pore size (pore diameter) in the range of 0.4 μm to 5.0 μm and comprising pores having a surface pore diameter < 10 μm and having an average grain size < 0.05 mm;
ii) purging the graphite substrate with nitrogen in the process chamber until the oxygen content in the process chamber is about 5.0%;
iii) heating the porous graphite substrate in a furnace to a temperature of at least about 1000 ℃;
iv) continuing to purge the porous graphite substrate with nitrogen and heating it to a temperature of > 1000 ℃ until the oxygen content is 0.5% or less.
Such a process may be performed in a graphite-coated process chamber. The process chamber may comprise a holding element on which the graphite element to be treated can be mounted. It is preferred that the contact point between the graphite element and the holding element is kept as small as possible. The process chamber may be heated. Such process chambers are known in principle.
The process may further comprise the following step v) following step iv): reducing stress in the activated porous graphite substrate by maintaining the activated porous graphite substrate at a temperature > 1000 ℃ to anneal the activated porous graphite substrate.
Dust or loose particles may be removed from the surface of the activated porous graphite substrate. However, it is particularly preferred that the activated porous graphite substrate obtained by the activation process is directly subjected to a chemical vapor deposition treatment, such as described below. Thus, after step iv) or optional step v), the aforementioned process preferably comprises the following further step vi): the activated porous graphite substrate is directly subjected to CVD treatment. Therein, it is particularly preferred to omit any cleaning step between the activation process and the CVD process, such as for example described in US 3,925,577.
Thus, another aspect of the invention relates to a process for manufacturing an activated graphite substrate having a modified surface porosity, the process comprising the following specific process steps
i) Positioning a graphite substrate in the process chamber, the graphite substrate having an open porosity and comprising pores having an average pore size (pore diameter) in the range of 0.4 μm to 5.0 μm and comprising pores having a surface pore diameter < 10 μm and having an average grain size < 0.05 mm;
ii) purging the graphite substrate with nitrogen in the process chamber until the oxygen content in the process chamber is about 5.0%;
iii) heating the porous graphite substrate in the furnace to a temperature of at least about 1000 ℃;
iv) continuing to purge the porous graphite substrate with nitrogen and heating it to a temperature of > 1000 ℃ until the oxygen content is < 0.5%;
v) optionally annealing the activated porous graphite substrate resulting from step iv) at a temperature > 1000 ℃ to reduce stress in the activated porous substrate;
vi) directly subjecting the activated porous graphite substrate of step iv) or v) to a CVD treatment without a preceding cleaning step.
In one aspect of the invention, the activated porous graphite substrate, which is directly subjected to a CVD process without removing dust or loose particles, may comprise a powder layer on the surface, which then predominantly comprises carbon powder or dust. The porous graphite substrate resulting from step iv) or v) may comprise such a surface powder layer having a thickness of 1 μm to 15 μm, preferably 2 μm to 10 μm, preferably 3 μm to 7 μm, preferably > 1 μm, preferably 2 μm. Thus, the activated porous graphite substrate directly subjected to the CVD treatment in step vi) preferably exhibits a respective surface powder layer.
Such loose powder layers surprisingly prove to have a positive effect on the SiC coating in the CVD process. Without being bound by theory, it is believed that the loose powder layer provides an improved nucleation surface to enhance the growth of crystalline SiC and further accelerate SiC formation.
In step ii) of the activation process described above, the nitrogen is preferably purged until the oxygen content in the process chamber is about 3.0%, preferably about 2.5%. In step iv), the purging with nitrogen and heating is preferably continued until the oxygen content is reduced to ≦ 0.3%, preferably ≦ 0.2%, preferably ≦ 0.1%.
An oxygen/carbon monoxide meter Bacharach model 0024-.
Similar to the purification process described above, it is critical that the oxygen content in step ii) is higher than the content defined herein before heating the porous graphite member in step iii). At higher oxygen contents, the graphite can burn off and the pore structure is at least partially destroyed. If the oxygen content in step ii) is below the content defined herein before heating the porous graphite member in step iii), sufficient activation of the graphite substrate cannot be achieved.
Preferably, the temperature in steps iii) and iv) is between > 1000 ℃ and 1500 ℃, preferably between 1000 ℃ and 1200 ℃.
Process steps ii) to iv) are carried out until the defined oxygen content has been achieved.
Very preferably, the purified and chlorinated graphite component as described above is subjected to the present activation treatment. It is therefore particularly preferred that in the activation process the graphite substrate of step i) exhibits a chlorine content of at least about 20.00ppb wt., preferably at least about 40.00ppb wt., preferably at least about 60.00ppb wt.
In another aspect, the chlorine content in the porous graphite substrate used in step i) is at least about 30.00ppb wt., preferably at least about 40.00ppb wt., preferably at least about 50.00ppb wt.
On the other hand, the chlorine content in the porous graphite substrate used in step i) is in the range of about 20.00ppb to 250.00ppb by weight, preferably about 30.00ppb to 250.00ppb by weight, preferably about 40.00ppb to 250.00ppb by weight, preferably about 50.00ppb to 250.00ppb by weight.
On the other hand, the chlorine content in the porous graphite substrate used in step i) is in the range of about 20.00ppb wt. to 250.00ppb wt., preferably about 20.00ppb wt. to 200.00ppb wt., preferably about 20.00ppb wt. to 175.00ppb wt., preferably about 20.00ppb wt. to 165.00ppb wt.
Very particularly, the preferred chlorine content is present within the porous graphite substrate, particularly at a depth ≧ 50 μm below the major surface.
As mentioned above, the use of graphite substrates having such a chlorine content remaining within the graphite substrate facilitates further purification during the activation process of the present invention.
For the reasons set forth above, the porous graphite substrate of step i) of the activation process preferably has pore characteristics as defined above, such as in particular a small average pore size (diameter) and a low porosity as defined above.
For the reasons set forth above, the porous graphite substrate of step i) of the activation process preferably has a porosity as defined above.
For the reasons set forth above, the porous graphite substrate of step i) of the activation process preferably has a grain size and/or density as defined above.
The porous graphite substrate treated in the activation process described herein may be further purified to the residual chlorine content, as illustrated above. Thus, the activated porous graphite substrate resulting from the process described above may contain an amount of one or more of the following impurity elements
Calcium < 100.00ppb wt. -%,
magnesium < 100.00ppb by weight,
aluminum < 100.00ppb wt. -%,
titanium < 20.00ppb by weight,
chromium is < 200.00ppb wt. -%,
manganese < 20.00ppb by weight,
copper < 100.00ppb wt. -%,
iron < 20.00ppb wt. -%,
cobalt < 20.00ppb by weight,
nickel < 20.00ppb by weight,
zinc < 100.00ppb by weight,
molybdenum < 300.00ppb wt. -%;
preferably contains an amount of one or more of the following impurity elements
Calcium < 50.00ppb by weight,
magnesium < 50.00ppb by weight,
aluminum < 50.00ppb by weight,
titanium < 10.00ppb by weight,
chromium is less than 100.00ppb by weight,
manganese < 10.00ppb by weight,
copper < 50.00ppb wt. -%,
iron < 10.00ppb wt. -%,
cobalt < 10.00ppb by weight,
nickel < 10.00ppb by weight,
zinc < 50.00ppb by weight,
molybdenum < 150.00ppb wt.
The activated porous graphite substrate may have a purity of 98% or more, preferably 99% or more.
The activated porous graphite substrate may further have a total amount of impurities of 10.00ppm wt. or less, preferably 5.00ppm wt. or less, preferably 4.00ppm wt. or less.
Such CVD treatment can be carried out in the same process chamber if the activated porous graphite substrate is directly subjected to a chemical vapor deposition treatment. Then, if the temperature in the process chamber is > 1000 ℃ and the oxygen content in the process chamber is below 1.5%, introduction of H may begin 2 . For example, if such an oxygen content below 1.5% is reached in the process chamber, process step 2) of the CVD method described below may already be started.
By the activation process, the surface pore modification described above with enlarged surface pore size as defined above can be achieved.
The correspondingly treated graphite substrate has proven particularly suitable for supporting the formation of SiC tendrils in the CVD process using DMS described herein and for providing an improved substrate for the CVD process as described herein.
4. Deposition of silicon carbide (SiC) on porous graphite substrates by Chemical Vapor Deposition (CVD)
Another process step involves depositing SiC on a porous graphite substrate. Preferred porous graphite substrates are purified and chlorinated graphite members resulting from the purification process described above, and activated graphite substrates resulting from the activation process described above, which substrates exhibit modified increased surface porosity.
The key elements of the process of the present invention are the formation of an interfacial layer with SiC filling the pores of the porous graphite substrate and the subsequent deposition of SiC to form an outer silicon carbide layer on the porous graphite substrate, which is achieved by chemical vapor deposition of dimethyldichlorosilane. In principle, chemical vapor deposition ("CVD", also known as chemical vapor deposition "CVPD") is a well-known technique in the semiconductor industry for producing high-quality, high-performance solid materials, such as in particular thin films. Typically, the substrate is exposed to one or more volatile precursors that react and/or decompose on the substrate surface to produce the desired deposit. CVD is commonly used to deposit silicon, silicon dioxide, silicon nitride, and silicon carbide. Various organosilanes may be used as the volatile CVD precursor, among others, including simple organosilanes such as monomethylsilane, dimethylsilane, trimethylsilane and tetramethylsilane, which may be substituted with one or more halogen atoms, and chlorosilanes including, for example, methyldichlorosilane, methyltrichlorosilane, tetrachlorosilane (SiCl) 4 ) Dimethyldichlorosilane), and arylsilanes which may be substituted with halogen atoms. The most common CVD precursors used to deposit silicon carbide are trichlorosilane, tetrachlorosilane, and methyltrichlorosilane.
The properties and quality of the deposited SiC material, as well as its behavior in CVD processes, depend largely on the type of organosilane precursor material selected and on the particular CVD process conditions applied, as described, for example, by d.cagliostro and s.ricccitiello (1990) and by Byung Jin Choi (1997) (both cited above). As described, for example, by d.cagliostro and s.ricccitiello (1990), the volatility, transport properties, and reaction kinetics of components formed from precursor materials affect the ability to permeate, condense, and/or coat the porous media and thus affect morphology, densification, and/or mechanical properties. As further described in US2018/002236 cited above, proper selection of the porous substrate material is also critical to achieving Si infiltration into the pores. Too small porosity may hinder the introduction of Si raw material into a deeper region of the porous substrate, and too large pores may deteriorate the mechanical strength of the substrate. Byung Jin Choi (1997) further demonstrated the effect on the properties and quality of deposited SiC materials by varying specific process conditions (e.g., CVD temperature) and by using different organosilane CVD precursor materials.
The inventors of the present invention have surprisingly found that by using Dimethyldichlorosilane (DMS) as the CVD precursor, the advantageous product properties described herein can be obtained with the novel process of the present invention. Achieving improved properties of SiC materials deposited on porous graphite to form the improved SiC-coated articles described herein has proven possible with the specific selection of Dimethyldichlorosilane (DMS) as a CVD precursor in the novel process of the present invention, rather than, for example, the more common tetrachlorosilane, trichlorosilane, or methyltrichlorosilane (MTS, trichloromethylsilane). The new and improved SiC coated articles are characterized, for example, by the improved SiC materials described below having particular SiC grain and crystal sizes and a reduced content of amorphous SiC of substantially tetrahedral crystallinity, which improves the strength and hardness, particular SiC tendrils formation and pore filling of the deposited SiC discussed herein, wherein an interface layer having the described thickness and an improved outer SiC coating in intimate connection with the SiC tendrils is formed, thereby providing improved mechanical properties, uniformity and continuity, and the like.
Thus, another aspect of the invention relates to a CVD process with very specific CVD process conditions, which CVD process is suitable for providing a new and improved SiC coating and thus a new and improved SiC coated body.
In particular, the inventors of the present invention found that only in the presence of H 2 Dimethyl Dichlorosilane (DMS) as purge gasThe silane source or CVD precursor causes the formation of SiC whiskers that grow into the porous structure of the porous graphite substrate, thus extending into the graphite substrate, at the specific CVD process conditions under which SiC is deposited on the graphite substrate with an open porosity. Such SiC tendrils are characterized by substantially tetrahedral SiC crystals (as shown, for example, in fig. 10) that form a tightly connected crystalline SiC material in the form of root tendrils extending into the porous graphite substrate in lengths of at least 50 μm. As mentioned above, the improved SiC material deposited under the particular conditions of the CVD process of the present invention is characterized by being formed primarily as crystalline β -SiC (see, e.g., fig. 11), which forms tetrahedral crystals (see, e.g., fig. 10) and contains a small amount of amorphous SiC, as shown by the XRD pattern of fig. 11 with a very sharp β -SiC peak (111). The SiC tendrils are further tightly connected with the overlying SiC surface coating as shown for example in fig. 6b (reference numeral (7)). This achieves improved connectivity of the SiC surface layer to the graphite substrate and reduces flaking, peeling or warping.
This allows deposition of SiC coatings on porous graphite substrates with enhanced mechanical properties, such as improved mechanical properties, such as intimate connection (adhesion) of the SiC coating to the underlying substrate, high etch resistance, impact resistance, fracture toughness and/or crack resistance of the SiC coating and oxidation resistance of the coated body, as well as improved uniformity of the SiC coating.
Thus, another aspect of the invention relates to a process for manufacturing a silicon carbide (SiC) -coated body (or article), said process comprising the following steps
1) Positioning a porous graphite substrate in a process chamber, the porous graphite substrate having an open porosity with a porosity of 6% to 15% and comprising pores having a surface pore size of 10 μ ι η to 30 μ ι η;
2) in the presence of H 2 Heating the porous graphite substrate in the process chamber at atmospheric pressure to a temperature in the range of 1000 ℃ to 1200 ℃ as a purge gas;
3) dimethyl Dichlorosilane (DMS) and H 2 Is introduced into the process chamber for at least 30 minutes；
4) Depositing crystalline SiC grains in the openings of the graphite substrate in an injection phase by chemical vapor deposition and allowing the crystalline SiC grains to grow into substantially tetrahedral SiC crystals until a connected crystalline SiC material in the form of whiskers extending into the porous graphite substrate in a length of at least 50 μ ι η is formed;
5) optionally continuing the chemical vapor deposition until depositing a surface layer of SiC up to a thickness of 50 μm on the surface of the graphite substrate in the first growth stage, the SiC surface layer comprising substantially tetrahedral SiC crystals;
6) cooling the body obtained from step 5).
Preferably, in step 2), the temperature is from 1000 ℃ to < 1200 ℃, more preferably from 1100 ℃ to 1150 ℃. As can be seen in fig. 9, selecting a suitable temperature range in a CVD process affects SiC crystallization by affecting the crystal growth rate and the homogeneous nucleation rate. Within the optimal temperature range (shaded area in fig. 9), the balance between crystal growth and homogeneous nucleation is properly balanced, and substantially tetrahedral SiC having the crystal size defined herein and whisker formation can be achieved. Fig. 9 further shows that too high a temperature leads to melting and the formation of metastable material (amorphous SiC). Appropriate temperature ranges with well-balanced crystal growth rate and homogeneous nucleation rate have to be determined individually according to further process conditions, such as in particular according to the choice of organosilane source used as CVD precursor.
Pressure conditions also affect the balance of crystal growth rate and homogeneous nucleation rate. Low pressure supports low deposition rates and contributes to fewer and large nuclei. The inventors of the present invention have found that atmospheric pressure is suitable for achieving the effects described herein.
The inventors have further found that whisker formation is dependent on the CVD deposition time. Thus, in step 3), Dimethyldichlorosilane (DMS) and H are reacted 2 Is introduced into the process chamber for > 30 minutes. Preferably, Dimethyldichlorosilane (DMS) and H are introduced 2 For > 30 minutes and < 12 hours, preferably > 45 minutes and < 10 hours, more preferably for at least one hour, more preferably for <A period of 10 hours, preferably < 8 hours, preferably < 6 hours, preferably < 4 hours, preferably < 3 hours, most preferably within 1 to 2 hours. In a short time, the formation of whiskers according to the invention is hardly possible. Longer times become disadvantageous in view of process economics.
It is further preferred that in the process of the present invention DMS and H are used 2 Is performed at a total flow rate of 25slpm to 200slpm, preferably 40slpm to 180slpm, more preferably 60slpm to 160 slpm.
It is particularly preferred to deposit not only SiC tendrils in the pores of the graphite, but also a SiC coating on top of the surface of the graphite substrate with SiC-filled pores. Thus, step 5) is preferably carried out, although not mandatory. Of course, step 5) may be controlled to achieve a desired thickness of the SiC surface layer, for example, by varying the deposition time and/or the amount of DMS.
It has further proved that, surprisingly, the formation of SiC tendrils can be significantly improved or promoted if a preconditioning step is included before step 2) and then step 2) is carried out directly, wherein by using N in the preconditioning step 2 The process chamber is purged and heated to a temperature of 1000 deg.C or more, preferably 1000 deg.C to 1500 deg.C to pre-treat and activate the porous graphite substrate. In principle, this pre-treatment step is very similar to the graphite activation process described above. As mentioned above, the activation process and the CVD method are preferably combined and carried out in the same process chamber. Accordingly, such a preconditioning step preferably comprises purging the process chamber with nitrogen until the oxygen content in the process chamber is about 5.0%, followed by heating the process chamber to a temperature of at least about 1000 ℃, preferably > 1000 ℃ to 1500 ℃, preferably 1000 ℃ to 1200 ℃, until the oxygen content is ≦ 0.5%, preferably ≦ 0.3%, preferably ≦ 0.2%, preferably ≦ 0.1%.
An oxygen/carbon monoxide meter Bacharach model 0024-.
As mentioned above, it has further surprisingly been demonstrated that the specific porosity with specific pore size and porosity of the graphite substrate to be SiC coated by CVD plays an important role in achieving a coated article with the desired excellent mechanical properties, such as tight connection (adhesion) of the SiC coating to the underlying substrate, high etch resistance, impact resistance, fracture toughness and/or crack resistance of the SiC coating and oxidation resistance of the coated body. Thus, the graphite substrate to be coated with SiC should exhibit an open porosity having a small porosity of 6% to 15%, and should further include a sufficient amount of pores having an enlarged surface pore size of about 10 μm to 30 μm to facilitate SiC infiltration.
The graphite substrate to be coated with SiC in the process of the invention exhibits a porosity of ≥ 6% and ≤ 15% has proven particularly suitable for achieving SiC-coated articles having the desired properties.
Preferably, the graphite substrate to be coated with SiC in the process of the invention exhibits a porosity of > 6% to < 15%, or a porosity in the range of about 6% to about 14%, about 6% to about 13%, about 6% to < 13%, or a porosity in the range of > 6% to about 15%, about 7% to about 15%, between about 8% to 15%, about 9% to about 15%, about 10% to about 15%, about 11% to about 15%, or a porosity in the range of ≧ 11% to about 13%. Most preferred is a porosity of ≥ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%. This preferred range is likewise the preferred range in the purification and chlorination process and the activation process, both as described above, and is likewise the preferred range in the resulting product as described below.
For the reasons described above, it is further preferred that the porous graphite substrate has small pores, such as an average pore size (pore diameter) of 0.4 μm to 5.0 μm, preferably 1.0 μm to 4.0 μm, and comprises pores having an enlarged surface pore diameter of about 10 μm up to 30 μm, preferably up to 20 μm, preferably up to 10 μm.
For the reasons described above, it is further preferred that the porous graphite substrate has ≧ 1.50g/cm 3 Preferably ≥ 1.70g/cm 3 Preferably ≥ 1.75g/cm 3 The density of (2).
For the reasons described above, it is further preferred that the porous graphite substrate used in step 1) is an activated graphite substrate having a modified surface porosity having enlarged surface pores as described in detail above.
As mentioned above, the porosity, pore size/diameter or increased surface porosity and density according to the invention may be determined as indicated above, for example by known methods including determining porosity, in particular via SEM measurements.
The term "tendril" or "tendrils" as used in the present invention describes a deposited SiC material that grows to extend from the surface of the porous substrate into the pores and thus extends from the surface of the porous substrate into deeper regions thereof, for example in the tendrils, roots or tensile dimensions already described above, thereby providing a deep anchor or hook-like secure connection of the outer SiC layer extending above the surface of the porous substrate with the porous substrate. In order to achieve sufficient anchoring, the tendrils are allowed to grow into the pores until an average length of at least 50 μm is achieved.
Preferably, step 4) is carried out until a connected crystalline SiC material is formed in the form of whiskers extending with an average length of at least 75 μm, preferably at least 100 μm, preferably 75 to 200 μm.
The formation of whiskers extending into the pores of the graphite substrate in the implantation phase of step 4) in the process of the present invention causes the formation of so-called "interface layers". The term "interfacial layer" as used in the present invention describes a region or zone located between the porous graphite substrate and the SiC coating deposited on the surface of the porous graphite substrate, for example in step 5) and/or in step 8), as described below, and which is formed from porous graphite, wherein the pores are filled with the deposited SiC, i.e. SiC tendrils, as described herein. Thus, the interfacial layer of the SiC-coated article or body of the present invention comprises the porous graphite material of the porous graphite substrate, with SiC tendrils extending into the pores.
Preferably, step 4) is carried out until an interfacial layer having a thickness of at least 100 μm is formed.
The interfacial layer extends more or less vertically from the surface of the porous graphite substrate down into the porous graphite substrate and thus forms an interfacial layer or region. The interfacial layer preferably has a thickness of > 100 μm, more preferably at least 200 μm, more preferably from about 200 μm to about 500 μm.
In step 3) of the present invention, the heated porous graphite substrate is subjected to chemical vapor deposition to deposit silicon carbide in and on the porous graphite substrate. Wherein DMS and H according to step 3) 2 The mixture of (a) is preferably obtained by: h is to be 2 Introducing the gas into DMS tank to make H 2 Bubbling through DMS in the tank, and by pushing DMS and H from the top of the tank 2 To deliver the mixture into a process chamber.
Preferably, with DMS and H 2 Is performed at a total flow rate of 25slpm to 200slpm, preferably 40slpm to 180slpm, more preferably 60slpm to 160 slpm. More preferably, an amount of the mixture from 25slpm to 45slpm is introduced into the process chamber.
Preferably, H is 2 Guided through the DMS tank and combined with the DMS. Another amount of H may be added 2 Purge directly into the process chamber where it reacts with DMS and H 2 The mixture of (a) is combined.
For controlling DMS/H 2 The flow meter for the flow of the mixture may be a flow meter of a Sierra Instruments Digital MFC.
Heating and application of H may also be carried out prior to introduction of DMS 2 A further step of purification.
As mentioned above, argon is also a common purge gas in CVD processes, however, the inventors have found that whisker formation does not occur when argon is used as a purge gas in the CVD process of the invention (or any other process described herein). Thus, the process is preferably carried out in the absence of argon.
In a preferred further step e) of the CVD process of the invention, the CVD process is carried out by continuing with dimethyldichlorosilane and H 2 In the mixing ofChemical vapor deposition of the substance to further grow a SiC layer on the porous graphite substrate in the first growth stage, thereby covering the graphite substrate surface. As mentioned above, the thickness of such SiC coatings may vary, but surface layers of up to 50 μm are preferred.
Preferably, process step 5) is carried out until a surface layer of SiC of at least 30 μm, preferably at least 35 μm, preferably at least 40 μm, more preferably at least 45 μm thickness is deposited on the surface of the graphite substrate.
Such SiC-coated graphite substrates can be subjected to a further step of annealing the coated porous graphite substrate by maintaining the coated porous graphite substrate at a temperature > 1000 ℃ to reduce the stress in the SiC coating and in the porous graphite substrate.
Such an annealing step may also be carried out after the preconditioning step described above.
Accordingly, such an annealing step may be carried out in the following case
Before step 2) and/or after the preconditioning step described above (if present),
-and/or before step 6).
Since the graphite substrate member is positioned on the holding member, the contact point is not coated with SiC in the CVD process. Thus, in order to achieve a uniform and continuous SiC coating over the entire surface, the following process steps 7) and 8) can be carried out after step 6):
7) changing the position of the body resulting from step 6); and
8) repeating step 2) and growing Dimethyldichlorosilane (DMS) and H in a second growth stage 2 Is introduced into the process chamber, thereby depositing crystalline SiC grains by Chemical Vapor Deposition (CVD) on the surface of the porous graphite substrate resulting from step 6) and allowing the crystalline SiC grains to grow into substantially tetrahedral SiC crystals until an outer SiC surface layer is formed.
Preferably, the second growth phase according to step 8) is carried out under the same CVD conditions as in the implantation phase and the first growth phase. Thus, in principle, what is defined above in relation to the first growth phase also applies.
The annealing step described above can also be carried out before step 8) and/or before the cooling step 6). A similar cooling step is carried out after the second growth phase of step 8). After the cooling step, the coated body is preferably subjected to a quality check and optionally to a purification in order to remove loose particles and/or protruding crystals.
Preferably, however, the CVD process according to the invention is controlled such that the SiC layer deposited on the graphite substrate in the first growth phase in step 5) is thicker than the SiC layer deposited on the graphite substrate in the second growth phase in step 8) under the same conditions, in particular with the same amount of DMS and with the same deposition time. This can be achieved, for example, by carrying out the preconditioning step described above before step 2). This is certainly considered surprising since it would be considered that applying the same amount of DMS to the porous graphite of step 1) in the same time would produce a thinner SiC coating in the first growth stage, since DMS is required to form the SiC tendrils before the SiC coating is built, which takes some time to build the coating. Without being bound by theory, it is believed that the preconditioning step provides an activated surface of the graphite substrate that provides crystallization sites for the SiC crystals and thereby accelerates and promotes SiC formation in the pores and on the graphite surfaces. Such a preconditioning step may comprise the process steps i) to v) described above. It is believed that the layer of the surface powder formed on the graphite substrate in process steps i) to v) described above may serve as the activated surface of the graphite substrate subjected to the CVD treatment in step 1) above. The powder on the graphite surface can provide the crystallization point for the SiC crystal and accelerate and promote SiC formation.
In the so-called "injection phase", very small SiC grains are formed in the open pores of the porous graphite substrate, and such SiC grains are grown into SiC crystals of β -SiC having substantially tetrahedral crystallinity to form so-called "whiskers" in the pores.
After filling the pores, small SiC grains are deposited on the upper surface of the graphite substrate to begin building up the outer SiC layer in the so-called "growth phase". Small SiC grains are allowed to grow into SiC crystals to form the outer SiC layer.
According to the invention, the term "SiC grain" or "SiC grains" refers to very small crystalline particles formed and deposited in the chemical vapor deposition in steps 4) and 5) and 8) by using dimethyldichlorosilane, and which mainly comprise silicon carbide. Such SiC grains according to the invention are crystalline and exhibit an average grain size < 2 μm.
In contrast to the SiC grains defined above, according to the invention, the term "SiC crystal" or "SiC crystals" refers to the larger crystalline SiC particles and they are formed in steps 4) and 5) and 8) by allowing the deposited SiC grains to grow. Similarly, such SiC crystals according to the present invention mainly contain silicon carbide and exhibit an average particle size of 2 μm or more. Preferably, the SiC crystals according to the invention exhibit an average particle size of > 2 μm. It is further preferred that the SiC crystal according to the present invention exhibits an average particle size of not more than 30 μm. More preferably, the SiC crystals according to the present invention exhibit an average particle size in the range of about. gtoreq.2 μm to. gtoreq.30 μm.
The average particle size according to the present invention can be determined by known methods, such as SEM as indicated above.
Thus, in another aspect of the process of the invention, the implantation phase of step 4) is controlled to achieve the formation of (crystalline) SiC grains formed in the pores during the implantation phase with an average grain size observable to be < 10 μm, such as in particular < 7 μm, more in particular < 5 μm or even < 4 μm or < 3 μm or even < 2 μm. Furthermore, the injection phase of step 3) is controlled to achieve the formation of SiC crystals having an average grain size of not more than 30 μm (≧ 2 μm to ≦ 30 μm), preferably not more than 20 μm (≧ 2 μm to ≦ 20 μm), preferably not more than 10 μm (≧ 2 μm to ≦ 10 μm) formed in the pores during the injection phase by allowing SiC grains to grow.
In another aspect of the process of the invention, the first and second growth stages of steps 5) and 8) are controlled to achieve formation of (crystalline) SiC grains having an average grain size observable at < 10 μm, such as in particular ≦ 7 μm, more in particular ≦ 5 μm or even ≦ 4 μm or ≦ 3 μm or even ≦ 2 μm, on the surface of the graphite substrate during the growth stage, and to allow SiC grains to grow to form SiC crystals having an average grain size of no more than 30 μm, preferably no more than 2 μm to ≦ 30 μm, preferably no more than 20 μm (≧ 2 μm to ≦ 20 μm), preferably no more than 10 μm (≧ 2 μm to ≦ 10 μm) on the graphite substrate during the growth stage to form the outer SiC layer.
During the injection phase, a certain amount of SiC grains may also have formed on the graphite surface.
Preferably, the substantially tetrahedral SiC crystals in the pores exhibit an average particle size < 10 μm, preferably < 7 μm, preferably < 5 μm, preferably < 4 μm, preferably < 3 μm, preferably < 2 μm.
Preferably, the substantially tetrahedral SiC crystals formed as a surface coating in the growth phase exhibit a larger particle size, preferably an average particle size of ≧ 10 μm, preferably ≧ 10 μm to 30 μm. This may be due to the space given by the pore size limiting crystal growth within the pores.
Furthermore, surprisingly, under the selected process conditions of the present invention, the deposited SiC proved to be substantially stoichiometric SiC having a Si: C ratio of 1: 1.
Furthermore, the process according to the invention is preferably controlled to deposit on the pores and/or surfaces of the graphite substrate a layer having a theoretical density corresponding to or very close to SiC, i.e. 3.21g/cm 3 SiC of the density of (a). Preferably, the deposited SiC has at least 2.50g/cm 3 Preferably, the deposited SiC has a density of at least 2.50g/cm 3 To 3.21g/cm 3 More preferably in the range of 3.00g/cm 3 To 3.21g/cm 3 A density within the range of (1).
In the process according to the invention, the CVD deposition is preferably carried out until the density of whiskers (amount of whiskers per unit area) formed in the interface layer is ≥ 6% and ≤ 15%, preferably 6% to 13%, more preferably 6% to ≤ 12%, more preferably 9% to 11.5%.
According to another aspect of the invention, a relatively high degree of hole filling with the deposited SiC material has proven to be advantageous in achieving the desired superior mechanical properties as described above. Thus, in a preferred embodiment of the process of the present invention, the implantation phase of step 4) is carried out until at least about 70% of the walls of the opening of the graphite substrate are coated with the deposited SiC material. For the sake of clarity, it should be noted that this should neither define 70% of the open porous substrate or 70% of the total amount of pores of the porous substrate to be filled with SiC, nor 70% of the volume of the pores to be filled with SiC. The hole filling degree according to the invention relates to the degree of coating of the inner walls of the open holes, wherein preferably at least 70% of the inner walls of the open holes are coated with the deposited SiC coating.
More preferably, the implantation phase of step 4) is carried out until at least about 75%, 80%, 85%, 90% of the inner wall of the opening is coated with the deposited SiC material.
On the other hand, with the CVD method according to the present invention, SiC can be deposited on the porous graphite substrate and in the open pores thereof so as to have a pore filling degree according to the above definition (i.e., SiC coating degree of the inner walls of the pores) of 80% or more up to a depth of about 10 μm from the main surface of the coated graphite.
With the CVD method according to the invention, SiC can be deposited on the porous graphite substrate and in the open pores thereof so as to have a pore filling degree according to the above definition (i.e., SiC coating degree of the inner walls of the pores) still ≧ 60% at a depth of between about 50 μm and about 10 μm from the main surface of the coated graphite.
With the CVD method according to the invention, SiC can be deposited on the porous graphite substrate and in the open pores thereof so as to have a pore filling degree according to the above definition (i.e., SiC coating degree of the inner walls of the pores) of about 50% at a depth of between about 100 μm and about 50 μm from the main surface of the coated graphite.
With the CVD method according to the invention, SiC can be deposited on the porous graphite substrate and in the open pores thereof so as to have a pore filling degree according to the above definition (i.e., SiC coating degree of the inner walls of the pores) of about 40% at a depth of between about 200 μm and about 100 μm from the main surface of the coated graphite.
At a depth of ≥ 100 μm, the hole filling degree according to the above definition is up to 50%.
At a depth of ≥ 200 μm, the hole filling degree according to the definition above is up to 40%.
As indicated above, the hole filling degree according to the present invention can be determined by SEM measurements.
As mentioned above, another aspect of the process of the present invention relates to the formation of so-called whiskers that behave like SiC-coated anchors in a porous substrate.
The process of the invention is specifically controlled to deposit a SiC coating in the form of a uniform and continuous substantially impermeable layer onto the surface of the graphite substrate in steps 5) and 8). This means that the SiC coating is in particular deposited so as to be substantially free of cracks, holes, chipping or other visible surface defects and to exhibit a continuous thickness over substantially the entire coated surface area (despite the lack of coating due to the retaining member in the first growth stage).
In the process according to the invention, the SiC material deposited in the pores in step 4) and/or on the surface in steps 5) and/or 8) contains at least 90 wt.% pure silicon carbide (SiC). Preferably, the SiC material deposited in steps 4), 5) and/or 8) comprises at least 91 wt.%, at least 92 wt.%, at least 93 wt.%, at least 94 wt.%, at least 95 wt.%, or at least 96 wt.% silicon carbide (SiC). More preferably, the SiC material deposited in steps 4), 5) and/or 8) contains at least 97 wt.% SiC, in each case relative to the total weight of the deposited SiC material.
The SiC material deposited in steps 4), 5), and/or 8) of the process of the present invention further comprises no more than about 10 wt.%, no more than about 9 wt.%, no more than about 8 wt.%, no more than about 7 wt.%, no more than about 6 wt.%, no more than about 5 wt.%, or no more than about 4 wt.% free Si. More preferably, the SiC material deposited in steps 4), 5) and/or 8) contains no more than about 3 wt.% free Si, in each case relative to the total weight of the deposited SiC material.
In the process according to the invention, the SiC material deposited in steps 4), 5) and/or 8) preferably comprises a high purity.
Surprisingly, under current process conditions, only a small amount of amorphous SiC is formed.
The aforementioned amounts of (pure) SiC and free Si relate to SiC material deposited in the pores of the graphite substrate, forming tendrils and interface layers, and/or SiC material deposited on the surface of the graphite substrate in the first and second growth stages, together forming an outer SiC layer. Thus, when referring to SiC in the meaning of e.g. "SiC layer", "SiC coating", "SiC coated body (article)", "SiC (pore) filler", "SiC grains" or "SiC crystal" and the like as used herein in any context with respect to CVD deposited SiC material in steps 4), 5) and/or 8), it does not necessarily mean pure SiC, but rather SiC material, which may comprise the above listed components in defined amounts, e.g. in particular wherein free SiC and other impurities may be present in addition to pure SiC.
In principle, the process of the present invention can be applied to any suitable graphite substrate. Preferably, a graphite substrate as described herein is used.
The process of the invention further comprises a step 6) of cooling the SiC-coated body (or article).
In another aspect of the invention, the inventors have surprisingly discovered that the purity of DMS used as a CVD precursor can affect the formation, crystallinity (quality), and length of the SiC tendrils described herein. In particular, the inventors have surprisingly found that the level of siloxane impurities in DMS used as a CVD precursor has an extraordinary effect on the desired SiC quality, crystal formation and hence whisker formation. It has also been found that the content of certain metal impurities, such as metal elements selected from the group consisting of Na, Mg, Al, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and M, affects the desired formation of SiC tendrils. Very particularly, it has been found that the presence of a certain content of impurities of metallic elements selected from Mn, Cu and/or Zn has a significant influence on the desired SiC tendril formation. More particularly, it has been found that the presence of a level of siloxane impurities along with a level of one or more of the metallic element impurities selected from Mn, Cu and/or Zn significantly affects the desired SiC tendril formation.
Without being bound by theory, it is believed that the presence of certain amounts of such siloxane impurities, as defined below, has a positive effect on the porosity of the graphite and the reduction of undesirable (toxic) metal impurities. The siloxane impurity introduces a certain amount of oxygen into the reaction system. As already described above in the context of activation of graphite substrates, it has been found that the oxygen content in the system has an effect on the surface porosity under the applied heating conditions. It is believed that oxygen originating from a certain amount of siloxane impurities exhibits an additional surface pore modifying effect in the CVD process, which facilitates the deep incorporation of silane into the pores of the activated graphite under the selected process conditions.
It is further believed that oxygen originating from the siloxane impurities traps and thereby deactivates the undesirable metal impurities in the DMS, and then allows the undesirable metal impurities to fall to the bottom of the tank and thereby "purify" the DMS to remove the undesirable metal content therefrom.
It has been observed that certain amounts of siloxane impurities cause the formation of precipitates or gels in the DMS tank, in the evaporator and/or in the vapor conduit system. Such gel formation occurs when a certain amount of such siloxane impurities and a certain amount of one or more of the above-mentioned metallic element impurities are present, such as in particular when a certain amount of such siloxane impurities and a certain amount of Mn, Cu and/or Zn are present. In addition, the residual moisture or residual water content can also further influence this gel formation. In view of the desired crystallinity of SiC, quality of SiC, and SiC tendril formation as described herein, it has been found that the amount of such siloxane impurities in the DMS precursor material for the CVD process as defined below is advantageous.
Accordingly, another aspect of the invention relates to a process for producing a silicon carbide (SiC) coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(B) at least one further component which is different from DMS and is a siloxane compound or a mixture of siloxane compounds,
wherein the content of the further component (B) is >0 wt.% to 2.00 wt.% with respect to the dimethyldichlorosilane precursor material.
Another aspect of the invention relates to a process for manufacturing a body coated with silicon carbide (SiC) in a Chemical Vapor Deposition (CVD) method using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises a siloxane compound (B) in a content of >0 wt.% to 1.500 wt.%, preferably >0 wt.% to < 1.040 wt.%, preferably >0 wt.% to 1.000 wt.%, preferably >0 wt.% to 0.900 wt.%, preferably >0 wt.% to 0.850 wt.%, preferably >0 wt.% to 0.800 wt.%, preferably >0 wt.% to 0.750 wt.%, preferably >0 wt.% to 0.700 wt.%, preferably >0 wt.% to 0.600 wt.%, preferably >0 wt.% to 0.500 wt.%.
Another aspect of the invention relates to a process for producing a silicon carbide (SiC) coated body in a Chemical Vapor Deposition (CVD) method using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises a siloxane compound (B) in an amount of >0 wt.% to not more than 0.500 wt.%, preferably >0 wt.% to not more than 0.450 wt.%, preferably >0 wt.% to not more than 0.400 wt.%, preferably >0 wt.% to not more than 0.375 wt.%.
Another aspect of the invention relates to a process for producing a body coated with silicon carbide (SiC) in a Chemical Vapor Deposition (CVD) method using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises >0 wt.% to 1.000 wt.%, preferably >0 wt.% to 0.850 wt.%, preferably >0 wt.% to 0.800 wt.%, preferably >0 wt.% to 0.750 wt.%, preferably ≦ 0.725 wt.%, preferably ≦ 0.710 wt.%, preferably >0 wt.% to < 700 wt.% of 1, 3-dichloro-1, 1,3,3, -tetramethyldisiloxane.
Another aspect of the invention relates to a process for producing a body coated with silicon carbide (SiC) in a Chemical Vapor Deposition (CVD) method using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises >0 wt.% to 0.200 wt.%, preferably >0 wt.% to 0.150 wt.%, preferably >0 wt.% to 0.140 wt.%, preferably >0 wt.% to 0.130 wt.%, preferably >0 wt.% to 0.120 wt.%, preferably >0 wt.% to < 0.110 wt.%, preferably >0 wt.% to < 0.100 wt.% of 1, 3-dichloro-1, 1,3,5,5,5, -hexamethyltrisiloxane.
Another aspect of the invention relates to a process for producing a silicon carbide (SiC) coated body in a Chemical Vapor Deposition (CVD) method using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises >0 wt.% to 0.200 wt.%, preferably >0 wt.% to 0.190 wt.%, preferably >0 wt.% to 0.180 wt.%, preferably >0 wt.% to 0.170 wt.%, preferably >0 wt.% to 0.160 wt.%, preferably 0 wt.% to < 0.150 wt.% octamethylcyclotetrasiloxane.
In addition, the metal element impurities can have an effect on the formation and length of SiC tendrils, for example, as explained above.
Accordingly, another aspect of the invention relates to a process for producing a silicon carbide (SiC) coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(C) a metal element selected from the group consisting of: na, Mg, Al, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and W,
wherein the content of metal element (C) is 30.00ppm wt. or less, preferably 25.00ppm wt. or less, preferably 20.00ppm wt. or less with respect to the dimethyldichlorosilane precursor material.
Another aspect of the invention relates to a process for producing a silicon carbide (SiC) -coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(C) a metal element selected from the group consisting of Mn,
wherein the content of Mn metal element (C) is < 150ppb wt.%, preferably < 100ppb wt.%, preferably < 50ppb wt.%, preferably < 40ppb wt.%, preferably < 30ppb wt.%, preferably < 20ppb wt.%, with respect to the dimethyldichlorosilane precursor material, preferably the content of Mn is between > 0ppb wt. and 40ppb wt.
Another aspect of the invention relates to a process for producing a silicon carbide (SiC) -coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(C) a metal element selected from the group consisting of Cu,
wherein the content of the Cu metal element (C) is < 50ppb wt.%, preferably < 45ppb wt.%, preferably < 40ppb wt.%, preferably < 35ppb wt.%, preferably < 30ppb wt.%, preferably < 25ppb wt.%, with respect to the dimethyldichlorosilane precursor material, preferably the content of Cu is between > 0ppb wt. and 25ppb wt.
Another aspect of the invention relates to a process for producing a silicon carbide (SiC) -coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(C) a metallic element selected from the group consisting of Zn,
wherein the content of Zn metal element (C) is < 50ppb wt.%, preferably < 45ppb wt.%, preferably < 40ppb wt.%, preferably < 35ppb wt.%, preferably < 30ppb wt.%, preferably < 25ppb wt.%, with respect to the dimethyldichlorosilane precursor material, preferably the content of Zn is between > 0ppb wt. and 25ppb wt.
Another aspect of the invention relates to a process for manufacturing a silicon carbide (SiC) -coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as the main component, and
(C) the metal elements of Mn, Cu and Zn,
wherein the contents of the Mn, Cu and Zn metallic elements (C) are the contents defined in the above-mentioned aspects.
Another particular aspect of the invention relates to a process for producing a silicon carbide (SiC) -coated body in a Chemical Vapor Deposition (CVD) process using a dimethyldichlorosilane precursor material, wherein the dimethyldichlorosilane precursor material comprises
(A) Dimethyldichlorosilane (DMS) as a major component;
(B) at least one further component different from DMS and being a siloxane compound or a mixture of siloxane compounds as defined in any of the aspects described above; and
(C) one or more of the above defined metallic elements, preferably Mn, Cu and Zn,
wherein the content of the siloxane component (B) is as defined in any one of the above-described aspects, and the content of the metal element (C), such as preferably Mn, Cu, and Zn, is as defined in any one of the above-described aspects.
On the other hand, DMS with a defined purity is used in particular in chemical vapor deposition processes which use H 2 As a purge gas. Preferably, wherein the dimethyldichlorosilane precursor material is reacted with H 2 Is conveyed into the reaction chamber. Additionally, the dimethyldichlorosilane precursor material and H may be obtained, among others, by 2 The mixture of (a): h is to be 2 Introducing a gas into a tank containing a dimethyldichlorosilane precursor material to form H 2 Bubbling through the tank, and mixing the dimethyldichlorosilane precursor material with H by pushing the mixture from the top of the tank 2 Is conveyed into the reaction chamber.
On the other hand, the dimethyldichlorosilane precursor material is also characterized by a certain content of one or more of the following elements
Calcium < 60.00ppb by weight,
magnesium < 10.00ppb by weight,
aluminum < 12.00ppb by weight,
titanium < 1.00ppb by weight,
chromium is < 60.00ppb by weight,
iron < 25000ppb by weight,
cobalt < 1.00ppb by weight,
nickel < 30.00ppb by weight,
zinc < 40.00ppb by weight,
molybdenum < 10.00ppb wt.
Another aspect of the invention relates to the process described herein, wherein a dimethyldichlorosilane precursor material is used to deposit silicon carbide on a porous graphite substrate having an open porosity of 6% or more and 15% or less, preferably 6% to 13%, more preferably 11% to 13%, more preferably 6% to 15%, preferably 6% or more and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
Thereby, a silicon carbide coated body may be obtained, characterized by a connected crystalline SiC material comprising substantially tetrahedral crystalline SiC, and in particular a connected crystalline SiC material comprising substantially tetrahedral crystalline SiC in the form of tendrils extending in a length of at least 50 μm as described herein.
The DMS purity defined is similarly suitable and preferred in the CVD processes described above.
The inventors of the present invention have further discovered that by specific selection of the CVD conditions and substrate materials described herein, the CVD process can be controlled to deposit substantially stoichiometric SiC on the substrate and in whisker form, characterized by a Si: C ratio of 1: 1.
Thus, another aspect of the invention relates to a method of using graphite having an open porosity as a substrate and dimethyldichlorosilane as a silane source and H in a Chemical Vapor Deposition (CVD) process 2 As a purge gas to form substantially stoichiometric amountsIn a process for manufacturing a silicon carbide (SiC) -coated body, wherein the CVD process is carried out at atmospheric pressure at a temperature in the range of 1000 ℃ to 1200 ℃, preferably in the range of 1000 ℃ to < 1200 ℃, preferably 1100 ℃ to 1150 ℃.
The CVD process is preferably carried out for a period of at least 30 minutes, preferably for a period of > 30 minutes and < 12 hours, preferably > 45 minutes and < 10 hours, more preferably for a period of at least one hour, more preferably for < 10 hours, preferably for < 8 hours, preferably for < 6 hours, preferably for < 4 hours, preferably for < 3 hours, most preferably for a period within 1 to 2 hours.
Preferably, DMS and H 2 Is performed at a total flow rate of 25slpm to 200slpm, preferably 40slpm to 180slpm, more preferably 60slpm to 160 slpm.
The inventors of the present invention have surprisingly found that under the present process conditions, substantially stoichiometric amounts of silicon carbide are deposited. The substantially stoichiometric silicon carbide is further preferably deposited in the form of (crystalline) SiC grains having an average grain size < 10 μm, in particular < 7 μm, more in particular < 5 μm or even < 4 μm, or < 3 μm or even < 2 μm. The SiC crystal grains can grow to form SiC crystals having an average particle size of at most 30 μm (. gtoreq.2 μm to. ltoreq.30 μm), preferably not more than 20 μm (. gtoreq.2 μm to. ltoreq.20 μm), preferably not more than 10 μm (. gtoreq.2 μm to. ltoreq.10 μm).
Preferably, the substantially stoichiometric SiC crystals in the pores exhibit an average particle size of < 10 μm, preferably < 7 μm, preferably < 5 μm, preferably < 4 μm, preferably < 3 μm, preferably < 2 μm.
Preferably, the substantially stoichiometric SiC crystals formed as the surface coating exhibit a relatively large particle size, preferably an average particle size of ≧ 10 μm, preferably ≧ 10 μm to 30 μm. This may be due to the space given by the pore size limiting crystal growth within the pores.
However, it is preferred to deposit SiC having smaller grains and crystal sizes because smaller grains and crystals form a higher density SiC coating, while larger grains and crystals form a lower density SiC coating. Therefore, it is desirable to deposit substantially stoichiometric silicon carbide. The amount of free Si in the deposited SiC is preferably controlled within the ranges defined herein, thereby achieving the desired grain and crystal sizes as defined above.
In another of its aspects, the process is carried out in particular without addition of methane gas and/or without use of argon, so it is preferred to exclude the presence of methane and/or argon. This is important because when DMS is used, the presence of methane gas or argon can adversely affect the formation of stoichiometric SiC.
In another aspect thereof, the process is particularly carried out without the use of any additional silane source other than dimethyldichlorosilane. Favorable SiC properties, crystal size and quality can be achieved with DMS as the sole organosilane source.
In another of its aspects, the process is carried out, in particular, by reacting dimethyldichlorosilane with H 2 Is conveyed into the reaction chamber.
In another of its aspects, the process is carried out in particular by using dimethyldichlorosilane and H 2 Is carried out by a mixture obtained by: h is to be 2 Introducing gas into the tank containing dimethyldichlorosilane to make H 2 Bubbling through the tank, and by pushing dimethyldichlorosilane and H from the top of the tank 2 To convey the mixture into a reaction chamber.
In another of its aspects, the process is especially carried out using a DMS comprising an amount of the (total) siloxane impurities defined above, such as >0 to 2.000 wt.%, preferably >0 to 1.500 wt.%, preferably >0 to < 1.040 wt.%, preferably >0 to 1.000 wt.%, preferably >0 to 0.900 wt.%, preferably >0 to 0.850 wt.%, preferably >0 to 0.800 wt.%, preferably >0 to 0.750 wt.%, preferably >0 to 0.700 wt.%, preferably >0 to 0.600 wt.%, preferably >0 to 0.500 wt.%.
In another of its aspects, the process is carried out in particular using DMS comprising a content of:
mn metal element < 150ppb wt., preferably < 100ppb wt., preferably < 50ppb wt., preferably < 40ppb wt., preferably < 30ppb wt., preferably < 20ppb wt.; and/or
(ii) a Cu metal element of < 50ppb wt.%, preferably < 45ppb wt.%, preferably < 40ppb wt.%, preferably < 35ppb wt.%, preferably < 30ppb wt.%, preferably < 25ppb wt.%; and/or
-Zn metal element < 50ppb wt.%, preferably < 45ppb wt.%, preferably < 40ppb wt.%, preferably < 35ppb wt.%, preferably < 30ppb wt.%, preferably < 25ppb wt.%.
In another aspect thereof, the process is carried out by depositing SiC on a porous graphite substrate, in particular from dimethyldichlorosilane as precursor material.
The porous substrate is advantageous in order to positively influence (trigger) the nucleation and formation of the desired stoichiometric substantially tetrahedral SiC crystals. Without being bound by theory, it is believed that the porous substrate surface provides a suitable basis to promote and support nucleation and crystallization of the deposited SiC at the desired quality.
Thus, it has proven advantageous to use a porous surface to deposit SiC thereon and thereby achieve the desired effects described herein.
The porosity characteristics of the substrate may be selected as described herein to achieve the above-described characteristics of the SiC coated substrate. As mentioned above, it is preferred that the porous graphite substrate comprises pores having a surface pore size of up to 30 μm, preferably 10 μm to 30 μm.
In another aspect thereof, the process is carried out using in particular a porous graphite substrate having an open porosity of ≥ 6% and ≤ 15%, preferably 6% to 13%, more preferably 11% to 13%. The use of graphite substrates with an open porosity of small porosity of 6% to 15%, preferably ≧ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5% has proven particularly advantageous.
Preferably, porous graphite as described anywhere herein is used.
It is particularly preferred to use the CVD process described herein wherein a dimethyldichlorosilane precursor material is used to deposit substantially stoichiometric silicon carbide with substantially tetrahedral SiC crystals on the surface of and in the pores of the porous graphite substrate to form a tightly connected crystalline SiC material in the form of whiskers extending from the porous graphite surface into the graphite substrate and tightly connected with the SiC surface coating.
In another aspect thereof, in the process, the amount of free Si in the SiC deposited on the graphite substrate includes no more than about 7 wt.%, preferably no more than about 5 wt.%, more preferably no more than about 3 wt.% free Si.
The inventors of the present invention further surprisingly found that under certain CVD conditions as described herein, the grain size of the SiC grains is related to the amount of DMS introduced into the reaction chamber. The introduction of a smaller amount of DMS surprisingly causes the formation of smaller grains and crystals, while the introduction of a larger amount of DMS surprisingly causes the formation of larger grains and crystals. Smaller grains and crystals further form a higher density SiC coating, while larger grains and crystals form a lower density SiC coating. Thus, CVD deposition can be controlled to provide multilayer SiC coatings with varying densities.
Thus, another aspect of the invention relates to a process for manufacturing a silicon carbide (SiC) -coated body comprising at least two SiC layers of different densities, said process comprising the following steps
A) Positioning a porous graphite substrate having an open porosity in a process chamber;
B) in the presence of H 2 Heating the porous graphite substrate in the process chamber at atmospheric pressure to a temperature in the range of 1000 ℃ to 1200 ℃ as a purge gas;
C) by mixing Dimethyldichlorosilane (DMS) and H in a first DMS amount 2 Is introduced into the process chamber to deposit on the surface of the graphite substrate in the first deposition stageDepositing crystalline SiC grains;
D) increasing or decreasing the amount of DMS and by adding DMS and H in a second amount of DMS 2 Is introduced into the process chamber to deposit crystalline SiC grains on the SiC-coated graphite substrate of step C) in a second deposition phase;
E) optionally repeating step D) one or more times, thereby performing one or more of the following additional steps: by combining DMS and H in one or more additional DMS amounts 2 Is introduced into the process chamber to deposit crystalline SiC grains on the SiC-coated graphite substrate in one or more additional deposition stages;
F) cooling the body obtained from step E).
In another aspect, the process further comprises the following step before step C)
B-2) reacting Dimethyldichlorosilane (DMS) with H 2 Is introduced into the process chamber for at least 30 minutes and crystalline SiC grains are deposited in the open pores of the graphite substrate in an injection phase by Chemical Vapor Deposition (CVD) and allowed to grow into SiC crystals until a connected crystalline SiC material in the form of whiskers extending into the porous graphite substrate in a length of at least 50 μm is formed.
In another aspect, the process comprises the following steps G) and H) after step F):
G) changing the position of the body resulting from step F); and
H) repeating step C) and optionally steps D) and E), thereby depositing crystalline SiC grains by Chemical Vapor Deposition (CVD) on the surface of the porous graphite substrate resulting from step F) and allowing the crystalline SiC grains to grow into substantially tetrahedral SiC crystals until one or more further SiC layers are formed; followed by cooling the body obtained from step H).
In another aspect of the process, in optional step E), the amount of DMS is gradually increased.
In another aspect of the process, in step D), the amount of second DMS is twice the amount of the first amount in step C).
In another aspect of the process, in step E), a third deposition phase is carried out with a third amount of DMS, which is three times the first amount in step C).
In another aspect of the process, in step E), the third deposition phase and the fourth deposition phase are carried out with a third DMS amount and a fourth DMS amount, wherein the fourth DMS amount is four times the first amount in step C).
In another aspect of the process, the amount of DMS in the deposition phase is controlled to achieve the formation of smaller SiC crystals with smaller grain sizes by introducing a reduced amount of DMS, and to achieve the formation of larger SiC crystals with larger grain sizes by introducing an increased amount of DMS.
In another aspect of the process, the thickness of the SiC coating deposited in the deposition phases is varied by performing the deposition phases for different periods of time.
In another aspect of the process, the porous graphite substrate of step A) has a porosity ≧ 6% and ≦ 15%, preferably 6% to 13%, more preferably 11% to 13%. More preferably, the porous graphite substrate of step A) has a porosity of ≥ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5% and/or comprises pores having a surface pore size of 10 μm to 30 μm.
More preferably, a porous graphite substrate as described anywhere herein is used.
In another aspect of the process, DMS and H 2 The mixture of (a) is obtained by: h is to be 2 Introducing the gas into DMS tank to make H 2 Bubbling through DMS in the tank, and by pushing DMS and H from the top of the tank 2 To deliver the mixture into a process chamber.
In another aspect of the process, the dimethyldichlorosilane for CVD deposition is characterized by having a content of siloxane impurities as defined above, preferably >0 to 2.00 wt.%, preferably >0 to 1.500 wt.%, preferably >0 to < 1.040 wt.%.
In another aspect of the process, the dimethyldichlorosilane used for CVD deposition is characterized by having a content of metallic element impurities as defined above, preferably Mn, Cu and Zn impurities as defined above.
More preferably, the dimethyldichlorosilane used for CVD deposition is characterized by having a content of siloxanes and metal impurities as defined in detail above.
In another aspect of the process, step B-2) is carried out until a connected crystalline SiC material is formed in the form of whiskers extending in a length of at least 75 μm, preferably at least 100 μm, preferably 75 to 200 μm.
In another aspect of the process, the implantation phase of step B-2) is carried out until an interface layer is formed, comprising porous graphite with SiC-filled pores and having a thickness of at least 50 μm, preferably at least 75 μm, preferably at least 100 μm, preferably at least 150 μm, preferably at least 200 μm, more preferably from about 200 μm to about 500 μm, wherein the interface layer is located between the graphite substrate and the SiC surface layer formed in steps C) to E) and H).
Preferably, the process is controlled to deposit substantially tetrahedral crystalline SiC having an average particle size of ≥ 10 μm, preferably ≥ 10 μm to 30 μm in one or more of steps C), D), E) and H) and/or the process is controlled to deposit substantially tetrahedral crystalline SiC having an average particle size of < 10 μm, preferably ≤ 7 μm, preferably ≤ 5 μm, preferably ≤ 4 μm, preferably ≤ 3 μm, preferably ≤ 2 μm in the pores of the graphite substrate in step B-2).
Preferably, the SiC deposition is carried out at a temperature in the range of 1000 ℃ to < 1200 ℃, preferably 1100 ℃ to 1150 ℃.
Preferably, the injection phase of step B-2) is carried out for a period of time of > 30 minutes and < 12 hours, preferably > 45 minutes and < 10 hours, more preferably for at least one hour, more preferably for < 10 hours, preferably for < 8 hours, preferably for < 6 hours, preferably for < 4 hours, preferably for < 3 hours, most preferably within 1 to 2 hours.
The SiC materials deposited herein are characterized by similar crystallinity, grain/crystal size and purity, etc., as described above. However, the density of SiC deposited in different steps varies.
Thus, with the process of the present invention, SiC coated articles can be provided wherein one or more selected surface regions of the graphite substrate are coated with an outer SiC coating. In steps E) and/or H), the SiC coating may also not be deposited on the entire surface of the porous graphite substrate, but only on selected and discrete regions of the substrate surface. This can be achieved, for example, by using a mask of a kind commonly used in established coating techniques.
Product III
Another aspect of the invention relates to products obtainable by the process of the invention, including intermediate components (such as graphite substrates) and SiC-coated articles.
1. Purified graphite component
Another aspect of the invention relates to a purified graphite component having a modified surface porosity obtainable by a process as described above.
Preferably, such a purified graphite member having a modified surface porosity has a chlorine content as defined above, which is preferably present in a porous graphite member as defined above.
Preferably, the purified graphite component of the present invention having modified surface porosity comprises pores having an expanded average pore size (pore diameter) and comprises pores having an expanded surface pore diameter of ≧ 10 μm.
The grain size of the graphite is generally unaffected by the process, and therefore the purified graphite component according to the invention having a modified surface porosity has an average grain size of < 0.05mm, preferably < 0.04mm, preferably < 0.03mm, preferably < 0.028mm, preferably < 0.025mm, preferably < 0.02mm, preferably < 0.018mm, preferably < 0.015 mm.
Preferably, such purified graphite components having modified surface porosity have an open porosity of ≧ 6% and ≦ 15%, preferably from about 6% to about 13%, preferably from about 11% to about 13%. More preferably, the purified graphite component has an open porosity of 6% to 15%, preferably ≧ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
Preferably, such a purified graphite component having a modified surface porosity has a density as defined above.
Preferably, such a purified graphite component having a modified surface porosity has a purity as defined above.
Purified graphite components having modified surface porosity as described herein may preferably be used as substrates in silicon carbide coated graphite articles.
Wherein the modified surface porosity may have the characteristics as described in detail above.
In particular, the purified graphite component with modified surface porosity as defined herein is suitable as a precursor for using Dimethyldichlorosilane (DMS) as silane source or CVD precursor, preferably with H 2 A substrate in a Chemical Vapor Deposition (CVD) process for depositing silicon carbide on a substrate as a purge gas, such as in particular a CVD process as described herein.
More particularly, the purified graphite component with modified surface porosity as defined herein is suitable as a precursor for using Dimethyldichlorosilane (DMS) as silane source or CVD precursor, preferably with H 2 A substrate in a Chemical Vapor Deposition (CVD) process for depositing silicon carbide in pores of a purified graphite substrate as a purge gas, such as in particular a CVD process as described herein.
For the reasons explained above, the purified graphite component having modified surface porosity as defined herein is particularly suitable as a substrate in a Chemical Vapour Deposition (CVD) process for depositing silicon carbide in the pores of an activated substrate, forming a connected substantially tetrahedral crystalline SiC material in the form of whiskers extending in a length of at least 50 μ ι η.
By depositing SiC on the purified graphite component as described herein, a graphite component having a silicon carbide layer on one or more surfaces and/or on one or more selected discrete surface regions may be provided.
Thus, such purified graphite components with modified surface porosity as described above are particularly suitable for the manufacture of articles for high temperature applications, susceptors and reactors, semiconductor materials, wafers.
2. Activated graphite substrate
Another aspect of the invention relates to an activated graphite substrate with modified surface porosity obtainable by a process as described above.
Preferably, such activated graphite substrate having modified surface porosity has a chlorine content as defined above, which is preferably present in the porous graphite substrate as defined above.
Preferably, such activated graphite substrates with modified surface porosity exhibit the surface pore modification with enlarged surface pore size described above.
In particular, such activated graphite substrates with modified surface porosity comprise pores with an enlarged average pore size (pore diameter) and comprise pores with a surface pore diameter of ≧ 10 μm, preferably ≧ 10 μm up to 30 μm.
Similar to what has been illustrated above, such activated graphite substrates with modified surface porosity have an average grain size < 0.05mm, preferably < 0.04mm, preferably < 0.03mm, preferably < 0.028mm, preferably < 0.025mm, preferably < 0.02mm, preferably < 0.018mm, preferably < 0.015 mm.
Preferably, such activated graphite substrates with modified surface porosity have an open porosity of a porosity of ≥ 6% and ≤ 15%, preferably from about 6% to about 13%, preferably from about 11% to about 13%, even more preferably from 6% to 15%, preferably ≥ 6% and < 15%, preferably from 6% to 13%, more preferably from 6% to < 12%, more preferably from 9% to 11.5%.
Preferably, such activated graphite substrate with modified surface porosity has a density as defined above.
Preferably, such activated graphite substrate with modified surface porosity has a purity as defined above.
Activated graphite substrates having modified surface porosity as described herein may preferably be used as substrates in silicon carbide coated graphite articles.
In particular, activated graphite substrates with modified surface porosity as defined herein are suitable as a precursor for using Dimethyldichlorosilane (DMS) as silane source or CVD precursor, preferably with H 2 A substrate in a Chemical Vapour Deposition (CVD) method of depositing silicon carbide on a substrate as a purge gas, such as in particular the CVD method as described herein.
More particularly, activated graphite substrates with modified surface porosity as defined herein are suitable as a precursor for using Dimethyldichlorosilane (DMS) as silane source or CVD precursor, preferably with H 2 A substrate in a Chemical Vapour Deposition (CVD) process, such as in particular the CVD process as described herein, of depositing silicon carbide, preferably forming connected substantially tetrahedral crystalline SiC material in the form of tendrils extending in a length of at least 50 μm, in the pores of an activated graphite substrate as a purge gas.
By depositing SiC on an activated graphite substrate as described herein, a graphite substrate having a silicon carbide layer on one or more surfaces and/or on one or more selected discrete surface regions may be provided.
Thus, such activated graphite substrates with modified surface porosity as described above are particularly suitable for the manufacture of articles for high temperature applications, susceptors and reactors, semiconductor materials, wafers.
Silicon carbide coated body
Another aspect of the invention encompasses a silicon carbide coated body (or article) obtained from the process as described above.
Preferably, another aspect of the invention relates to a silicon carbide coated body (or article) comprising
I) A porous graphite substrate having a porosity of 6% to 15%;
II) at least one SiC coating; and
III) an interface layer located between the graphite substrate I) and the SiC coating II), comprising porous graphite and having pores with an average surface pore diameter of 10 μm, wherein the pores are filled with a connecting crystalline SiC material in the form of whiskers having a length of at least 50 μm, which extends from the at least one SiC coating II) into the porous graphite substrate.
Another aspect of the invention relates to the silicon carbide coated body (or article) described above, wherein the pores in the interface layer III) are filled with a connecting crystalline SiC material in the form of whiskers extending in a length of at least 75 μ ι η, preferably at least 100 μ ι η, preferably 75 to 200 μ ι η. For the definition of the hole filling, reference is made to the above description.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the interface layer III) located between the graphite substrate I) and the SiC coating II) exhibits a thickness of at least 100 μm, preferably > 100 μm, more preferably at least 200 μm, even more preferably from about 200 μm to about 500 μm.
Another aspect of the invention relates to the silicon carbide coated body (or article) described above, wherein the porous graphite substrate I) exhibits a porosity of > 6% to < 15%, or a porosity in the range of about 6% to about 14%, about 6% to about 13%, about 6% to < 13%, or a porosity in the range of > 6% to about 15%, about 7% to about 15%, about 8% to 15%, about 9% to about 15%, about 10% to about 15%, about 11% to about 15%, or a porosity in the range of ≧ 11% to about 13%. Even more preferred is a porosity of ≧ 6% and < 15%, more preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
The porosity is related to the structure of graphite, and the pores are filled with SiC as described herein. However, only the graphite porosity is not affected or changed by the CVD process, and therefore, the current porosity may be considered "SiC-filled porosity".
Another aspect of the invention relates to the silicon carbide coated body (or article) described above, wherein the at least one SiC coating II) comprises > 90wt. of silicon carbide (SiC). Preferably, the SiC coating comprises at least 91 wt.%, at least 92 wt.%, at least 93 wt.%, at least 94 wt.%, at least 95 wt.%, or at least 96 wt.% silicon carbide. More preferably, the SiC coating comprises at least 97 wt.% of silicon carbide (SiC) relative to the total weight of the SiC coating in each case. As explained above, the silicon carbide is preferably substantially tetrahedral crystalline SiC.
Another aspect of the present invention relates to a silicon carbide coated body (or article) as described herein, wherein the at least one SiC coating II) further comprises no more than about 10 wt.%, no more than about 9 wt.%, no more than about 8 wt.%, no more than about 7 wt.%, no more than about 6 wt.%, no more than about 5 wt.%, or no more than about 4 wt.% free Si. More preferably, the SiC coating comprises no more than about 3 wt.% free Si, relative to the total weight of the SiC coating, in each case.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the SiC coating II) covering the graphite substrate I) is a uniform and continuous, substantially impermeable SiC layer.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the SiC coating II) overlying the graphite substrate is substantially free of cracks, voids, chipping, or other significant surface defects and/or exhibits a substantially continuous thickness throughout the coated surface region.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the interface layer III) located between the graphite substrate I) and the SiC coating II) is formed of porous graphite, wherein the pores comprise a filler of SiC, and wherein at least 70% of the walls of the open pores of the graphite are filled with SiC. For the definition of the hole filling, reference is made to the above description. As explained therein, the hole filling degree according to the invention relates to the degree of coating of the inner walls of the open holes, wherein preferably at least 70% of the inner walls of the open holes are coated with the deposited SiC coating.
More preferably, the interface layer III) comprises a pore filling of at least about 75%, 80%, 85%, 90% of the walls of the open pores. The hole filling degree may be determined as mentioned above.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the average grain size of the SiC crystals in the filled pores of the interface layer III) is < 10 μm, such as preferably > 2 μm to < 10 μm, and/or the average grain size of the SiC crystals of the outer coating ii) is not more than 30 μm, preferably ≧ 10 μm to 30 μm.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the interface layer III) located between the graphite substrate I) and the SiC coating II) is formed of porous graphite, wherein the pores comprise a filler of connected substantially tetrahedral crystalline SiC material in the form of extended tendrils, wherein the SiC material comprises > 90 wt.% silicon carbide (SiC). Preferably, the SiC material in the pores of the interfacial layer III) comprises at least 91 wt.%, at least 92 wt.%, at least 93 wt.%, at least 94 wt.%, at least 95 wt.%, or at least 96 wt.% silicon carbide. More preferably, the SiC material in the pores of the interface layer III) contains at least 97 wt.% SiC in each case relative to the total weight of the SiC material in the pore filling.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the interface layer III) located between the graphite substrate I) and the SiC coating II) is formed of porous carbon, wherein the pores comprise a filler of connected substantially tetrahedral crystalline SiC material in the form of extended whiskers, wherein the SiC material further comprises no more than about 10 wt.%, no more than about 9 wt.%, no more than about 8 wt.%, no more than about 7 wt.%, no more than about 6 wt.%, no more than about 5 wt.%, or no more than about 4 wt.% free Si. More preferably, the SiC material in the pores of the interfacial layer III) contains no more than about 3 wt.% free Si, relative to the total weight of SiC material in the pore filling, in each case.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the SiC in the pores and/or on the surface of the graphite substrate is substantially stoichiometric SiC having a Si: C ratio of 1: 1.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the SiC in the pores and/or on the surface of the graphite substrate has a density close to 3.21g/cm 3 The density of the theoretical SiC density of (1). Preferably, the deposited SiC has at least 2.50g/cm 3 Preferably at 2.50g/cm 3 To 3.21g/cm 3 More preferably in the range of 3.00g/cm 3 To 3.21g/cm 3 A density within the range of (1).
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein the density of whiskers (amount of whiskers per unit area) in the interface layer is ≥ 6% and ≤ 15%, preferably 6% to 13%, more preferably 6% to ≤ 12%, more preferably 9% to 11.5%.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein comprising a uniform, dense and/or uniformly distributed tendrils in the interface layer.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein, wherein tendrils are (intimately) connected with the surface coated SiC.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein comprising a SiC layer II) and optionally an interface layer III) on one or more selected and discrete surface regions of a graphite substrate.
The interfacial layer of the silicon carbide coated body of the present invention produces a Coefficient of Thermal Expansion (CTE) for the entire body that is averaged between the graphite substrate and the SiC coating. For example, in a silicon carbide coated body in which about 20% of the porous substrate is filled with SiC, the CTE mismatch between the substrate and the SiC layer may be reduced by about 20%. Accordingly, another aspect of the present invention is directed to a silicon carbide coated body as described herein having an improved coefficient of thermal expansion between the graphite substrate and the SiC coating. The CTE according to the invention can be determined by known methods.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein having an improved residual compressive load in the SiC layer, preferably higher than 190MPa, preferably higher than 50 MPa. The residual compressive load according to the present invention can be determined by known methods.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein having improved impact resistance. The impact resistance according to the invention can be determined by known methods.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein having improved fracture toughness. The fracture toughness according to the present invention can be determined by known methods.
Another aspect of the present invention relates to a silicon carbide coated body (or article) as described herein having improved spall, peel and/or warp resistance. The peel resistance (strength) can be determined by known methods, for example, as described in US2018/0002236 a 1.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein having improved adhesion between the graphite substrate I) and the SiC coating II). The adhesion between the graphite substrate I) and the SiC coating II) according to the invention can be determined by known methods.
Another aspect of the invention relates to a silicon carbide coated body (or article) as described herein that exhibits an improved relationship between the dimensions of the outer (upper) surface of the SiC coating and the dimensions of the interface layer. The relationship between the dimensions of the outer (upper) surface of the SiC coating and the dimensions of the interface layer according to the invention can be determined by known methods.
Another aspect of the invention relates to a silicon carbide coated body (or article) comprising
I-A) a porous graphite substrate having a porosity of 6 to 15% and comprising pores having a surface pore size of 10 to 30 μm, and
II-A) at least two SiC coatings of different densities, said at least two SiC coatings overlying a porous graphite substrate; and optionally
III-a) an interface layer located between the graphite substrate and the SiC coating, comprising porous graphite and pores filled with tightly connected substantially tetrahedral crystalline SiC material in the form of tendrils extending from the at least one SiC coating into the porous graphite substrate in a length of at least 50 μ ι η.
In another aspect of such multilayer SiC-coated articles, at least two SiC coatings II-A) are characterized by different crystal sizes.
In another aspect of such multilayer SiC coated articles, the graphite substrate has a porosity of ≧ 6% and ≦ 15%, preferably 6% to 13%, more preferably 11% to 13%, more preferably ≧ 6% and < 15%, preferably 6% to 13%, more preferably 6% to < 12%, more preferably 9% to 11.5%.
Preferably, the graphite substrate comprises pores having a surface pore size of up to 30 μm.
Preferably, the graphite substrate has an average pore size (pore diameter) of 0.4 μm to 5.0 μm, preferably 1.0 μm to 4.0 μm and comprises pores having a surface pore diameter of up to 30 μm, preferably up to 20 μm, preferably up to 10 μm, preferably pores having a surface pore diameter of 10 μm to 30 μm are present.
Preferably, the graphite substrate has an average grain size of < 0.05mm, preferably < 0.04mm, preferably < 0.03mm, preferably < 0.028mm, preferably < 0.025mm, preferably < 0.02mm, preferably < 0.018mm, preferably < 0.015 mm.
Preferably, the graphite substrate has ≥ 1.50g/cm 3 Preferably ≥ 1.70g/cm 3 Preferably ≥ 1.75g/cm 3 The density of (c).
In another aspect of such multilayer SiC coated article, there is an interface layer III-a) having pores filled with tightly connected substantially tetrahedral crystalline SiC material in the form of tendrils extending into the graphite substrate in a length of at least 75 μ ι η, preferably at least 100 μ ι η, preferably 75 to 150 μ ι η.
Use of
Another aspect of the invention relates to the use of purified, chlorinated and/or activated graphite components, and various silicon carbide coated bodies (or articles) obtainable by the process for manufacturing articles for high temperature applications, susceptors and reactors, semiconductor materials, wafers, etc. as described herein.
The invention is further illustrated by the figures and the following examples without being limited thereto.
Description of the figures and reference numerals
Fig. 1 shows a 680-fold magnified SEM image of a silicon carbide coated body according to the present invention having a graphite substrate (1) and SiC tendrils (4) and a SiC coating (2) in an interface layer (3) of the silicon carbide coated body. It can be seen that the interface layer (3) has a thickness of about 200 μm, i.e. the SiC tendrils (4) extend into the porous graphite substrate (1) with a length of at least 50 μm. The SiC coating (2) has a thickness of about 50 μm
Fig. 2 shows an SEM image 1250 times magnified of a silicon carbide coated body with a multi-layer SiC coating of different densities. The different SiC coatings exhibited different thicknesses, with the first SiC layer (2-a) having a thickness of about 43 μm, the second SiC layer (2-B) having a thickness of about 7 μm, and the third SiC layer (2-C) having a thickness of about 50 μm. The image further shows tendrils (4) in the interface layer (3) and SiC pore fillers in the form of SiC coatings of the inner walls of the pores (5).
Fig. 3 shows an SEM image of a silicon carbide coated body with a SiC coating (2) of approximately 100 μm thickness on a porous graphite substrate (1) without tendrils and interface layers. The openings (6) of the graphite substrate (1) are evident.
Fig. 4 shows an SEM image at 510 x magnification of a silicon carbide coated body having a SiC coating (2) of more than 50 μm thickness on a porous graphite substrate (1) but no tendrils and interface layers were formed due to the use of argon as purge gas. The openings (6) of the graphite substrate (1) are evident.
Fig. 5a and 5b show SEM images at 500 x magnification from a top view on SiC tendrils (4); thus, the graphite substrate is burned off in air, the morphology and distribution of the whiskers is visible, and the distribution of whiskers is very uniform and dense.
Fig. 6a shows a SEM image of a section view of SiC whiskers (4) magnified 390 times, which are very strongly connected to the SiC coating (2).
Fig. 6b shows a SEM image, magnified 2000 times, of a cross-sectional view of SiC tendrils (4) which are very strongly connected to the SiC coating (2).
Fig. 7a and 7b show 2000 x SEM images of porous graphite material having rather small pores, wherein the pores have a pore size < 10 μm, prior to the purification and activation process (pre-product) of the present invention.
Fig. 7c shows the pore distribution and average pore size of the porous graphite material prior to the purification and activation process (pre-product) of the present invention.
FIGS. 8a and 8b show 2000-fold magnified SEM images of porous graphite material after the activation process of the present invention, which clearly show the modified surface porosity with significantly enlarged surface pores (now including a large number of enlarged pores with a pore size/pore diameter of ≧ 10 μm).
Fig. 8c shows the pore distribution and average pore size of the porous graphite material after the activation process of the present invention, which shows increased porosity and increased average pore size compared to the graphite material before the activation process.
Fig. 9 shows the critical temperature dependence and its effect on SiC nucleation, growth and crystal formation in a CVD process.
Fig. 10 shows an SEM image at 3500 x magnification of the top view on the improved SiC material of the present invention, where substantial tetrahedral crystallinity and crystal sizes up to 10 μm to 30 μm are clearly visible.
Fig. 11 shows the XRD pattern of the improved SiC material of the present invention, showing a very sharp β -SiC crystallization peak and showing a very small by-product peak or amorphous SiC, which confirms the high purity and crystallinity of the SiC formed in the process of the present invention.
(1) Porous graphite substrate
(2) SiC coating
(2-A), (2-B), (2-C) SiC coating with different densities
(3) Interfacial layer
(4) Curling hair formed in the opening
(5) SiC coating on the inner wall of an opening
(6) Openings in graphite substrates
(7) Tight connection between tendrils and coating
(8) Tetrahedral crystal
VI. examples
Example 1 activation and Chlorination of graphite Member and tendril formation
The porous graphite member is activated, purified and subjected to the chlorination process described herein.
The following chlorine contents were measured in the chlorided graphite component:
| element(s) | Graphite member |
| Cl | 0.06ppm wt. |
The formation of activated graphite with increased surface porosity is shown in fig. 7 a-7 c compared to fig. 8 a-8 c. The SEM was prepared as described above.
In the CVD deposition method described herein, a chloridized graphite member is used as the porous graphite substrate (1).
In the CVD method, SiC tendrils (4) according to the invention are formed in the holes (6) of the correspondingly chloridized graphite substrate, as shown in fig. 1, fig. 2, fig. 3, fig. 4, fig. 5a, fig. 5b, fig. 6a and fig. 6 b.
The SiC characteristics and qualities described herein are shown in fig. 10 and 11.
Example 2 Effect of purge gas
Using H 2 A silicon carbide coated body was prepared by the process of the present invention as a purge gas.
As a comparative example, argon was used as purge gas.
As becomes apparent from fig. 1 and 4, the use of argon does not cause the formation of whiskers (4).
Example 3 multilayer SiC coating
A silicon carbide coated body was prepared using the process of the present invention, wherein the amount of DMS was varied to produce multilayer SiC coatings having varying densities (2-A), (2-B), (2-C), etc.
Wherein H is used in the deposition phase 2 The following DMS amounts were introduced as carrier gas into the process chamber of the laboratory scale test reactor:
| deposition | DMS amount | |
| 1. | About 0.5 g/ |
|
| 2. | About 1.0 g/min | |
| 3. | About 1.5 g/ |
|
| 4. | About 2.0 g/min |
The SiC coatings deposited in the first through fourth deposition phases exhibit varying crystal sizes that increase with increasing amounts of DMS, resulting in SiC coatings with progressively decreasing densities.
Another example is shown in fig. 2, which shows a SiC multilayer structure resulting from varying amounts of DMS.
Example 4 DMS purity (siloxane)
DMS with varying siloxane impurities a silicon carbide coated body was prepared by the process of the present invention.
DMS with the following siloxane impurities was used:
| siloxane compound | DMS sample A | DMS sample B | |
| 1, 3-dichloro-1, 1,3, 3-tetramethyldisiloxane | 0.193wt.％ | 0.103wt.％ | 0.710 |
| 1, 3-dichloro-1, 1,3,5,5,5, -hexamethyl trisiloxane | 0.042wt.％ | 0.072wt.％ | 0.110wt.％ |
| Octamethylcyclotetrasiloxane | 0.112wt.％ | 0.157wt.％ | 0.156wt.％ |
| Total amount of siloxane impurities | 0.389wt.％ | 0.375wt.％ | 1.04wt.％ |
| Total amount of impurities | 0.119wt.％ | 0.580wt.％ | 1.239wt.％ |
With DMS according to samples a and B, SiC whisker formation occurs according to the invention.
With DMS according to sample C, no sufficient formation of SiC whiskers occurred.
In addition, the following ranges were found to be effective for the desired whisker formation:
| total siloxane content | Whisker curl formation |
| ＞2.00wt.％ | - |
| 0.50 to 2.00wt. -%) | + |
| ＜0.50wt.％ | ++ |
"-" indicates that no or insufficient whisker formation occurs in the opening
"+" indicates moderate to low level of curl formation in the opening
"+ +" indicates that adequate curl formation occurs in the opening for optimum whisker formation
Example 5 DMS purity (Mn)
DMS with varying manganese impurities a silicon carbide coated body was prepared by the process of the present invention. DMS with the following manganese impurities was used:
| metallic element | DMS sample A | DMS sample B | DMS sample C |
| Manganese (Mn) | 2ppb wt. | 11ppb wt. | 150ppb wt. |
With DMS according to samples a and B, SiC whisker formation occurs according to the invention.
With DMS according to sample C, no sufficient formation of SiC whiskers occurred.
In addition, the following ranges were found to be effective for the desired whisker formation:
| total manganese content | Whisker curl formation |
| ≥150ppb wt. | - |
| From 40ppb by weight to 150ppb by weight. | + |
| ＜40ppb wt. | ++ |
"-" indicates that no or insufficient whisker formation occurs in the opening
"+" indicates moderate to low level of curl formation in the opening
"+ +" indicates that adequate curl formation occurs in the opening for optimum whisker formation
Example 6 DMS purity (Cu)
DMS with varying copper impurities a silicon carbide coated body was prepared by the process of the present invention. DMS with the following copper impurities was used:
| metallic element | DMS sample A | DMS sample B | DMS sample C |
| Copper (Cu) | 1ppb wt. | 18ppb wt. | 41ppb wt. |
With DMS according to samples a and B, SiC whisker formation occurs according to the invention.
With DMS according to sample C, no sufficient formation of SiC whiskers occurred.
In addition, the following ranges were found to be effective for the desired whisker formation:
| total copper content | Whisker curl formation |
| ≥50ppb wt. | - |
| 30ppb by weight to 50ppb by weight. | + |
| ＜30ppb wt. | ++ |
"-" indicates that no or insufficient whisker formation occurs in the opening
"+" indicates moderate to low level of curl formation in the opening
"+ +" indicates that adequate curl formation occurs in the opening for optimum whisker formation
Example 7 DMS purity (Zn)
DMS with varying zinc impurities a silicon carbide coated body was prepared by the process of the present invention.
DMS with the following zinc impurities was used:
| metallic element | DMS sample A | DMS sample B | DMS sample C |
| Zinc (Zn) | 1ppb wt. | 19ppb wt. | 42ppb wt. |
With DMS according to samples a and B, SiC whisker formation occurs according to the invention.
With DMS according to sample C, no sufficient formation of SiC whiskers occurred.
In addition, the following ranges were found to be effective for the desired whisker formation:
| total zinc content | Whisker curl formation |
| ≥50ppb wt. | - |
| From 30ppb by weight to < 50ppb by weight. | + |
| ＜30ppb wt. | ++ |
"-" indicates that no or insufficient whisker formation occurs in the opening
"+" indicates moderate to low level of curl formation in the opening
"+ +" indicates that adequate curl formation occurs in the opening for optimum whisker formation
Example 8 DMS purity (siloxane + manganese + copper + zinc)
The following ranges of total siloxane content in the presence of manganese, copper and zinc metal impurities were found to be effective for the desired whisker formation:
"-" indicates that no or insufficient whisker formation occurs in the opening
"+" indicates a moderate to low level of whisker formation in the opening
"+ +" indicates that adequate curl formation occurs in the opening for optimum whisker formation
Claims (15)
1. A method of making an activated graphite substrate having modified surface porosity, comprising:
i) positioning a porous graphite substrate in the process chamber, the porous graphite substrate having an open porosity, comprising pores having an average pore size in the range of 0.4 μm to 5.0 μm and comprising pores having a surface pore size < 10 μm, and having an average grain size < 0.05 mm;
ii) purging the porous graphite substrate with nitrogen in the process chamber until the oxygen content in the process chamber is about 5.0%;
iii) heating the porous graphite substrate in a furnace to a temperature of at least about 1000 ℃; and
iv) continuing to purge the porous graphite substrate with nitrogen and heating the porous graphite substrate to a temperature > 1000 ℃ in the process chamber until the oxygen content in the process chamber is ≦ 0.5%.
2. The method of claim 1, further comprising annealing the porous graphite substrate at a temperature > 1000 ℃ after purging the porous graphite substrate with nitrogen and heating the porous graphite substrate to a temperature > 1000 ℃ until the oxygen content is < 0.5%.
3. The method of claim 1, further comprising directly subjecting the porous graphite substrate to a chemical vapor deposition process without cleaning the porous graphite substrate prior to the chemical vapor deposition process after continuing to purge the porous graphite substrate with nitrogen in the process chamber and heating the porous graphite substrate to a temperature > 1000 ℃ until the oxygen content in the process chamber is < 0.5%.
4. The method of claim 1, wherein nitrogen is flowed in the process chamber until the oxygen content in the process chamber is about 3.0% prior to heating the porous graphite substrate in the furnace to a temperature of at least about 1000 ℃.
5. The method of claim 1, wherein after heating the porous graphite substrate to a temperature of at least about 1000 ℃ in the furnace, heating is continued until the oxygen content is reduced to ≦ 0.3%.
6. The method of claim 1, wherein the graphite substrate has a chlorine content of at least about 20.00ppb by weight prior to being placed in the process chamber, wherein the chlorine content is present in the graphite substrate at ≧ 50 μm below a major surface.
7. The method of claim 1, wherein the temperature is between 1000 ℃ and 1500 ℃ during heating the porous graphite substrate to a temperature > 1000 ℃ until the oxygen content in the process chamber is < 0.5% and continuing to purge with nitrogen in the process chamber.
8. The method of claim 1, wherein after continuing to purge the porous graphite substrate with nitrogen in the process chamber and heating the porous graphite substrate to a temperature > 1000 ℃ until the oxygen content in the process chamber is < 0.5%, the pores of the porous graphite substrate have an expanded average pore size compared to pores of the porous graphite substrate prior to being placed in the process chamber.
9. The method of claim 1, wherein the porous graphite substrate has a total amount of impurities of 10.00ppm by weight or less.
10. A process chamber component for high temperature processing a component, the process chamber component comprising:
a graphite substrate having an initial open porosity comprising pores having an average pore size in the range of 0.4 μ ι η to 5.0 μ ι η and comprising pores having a surface pore size < 10 μ ι η, the graphite substrate further having a later modified surface porosity comprising pores having an average pore size > 10 μ ι η at a surface of the graphite substrate, and the graphite substrate having an average grain size < 0.05 mm; and
a silicon carbide layer on a surface thereof, the silicon carbide layer being derived from dimethylchlorosilane, the silicon carbide layer extending into the pores of the later modified surface porosity,
wherein the silicon carbide layer comprises substantially tetrahedral crystalline silicon carbide tendrils having a length of at least 50 μm.
11. The process chamber component of claim 10, wherein the process chamber component has a chlorine content of at least about 20.00ppb by weight prior to modification of the pore size of the process chamber component, wherein the chlorine content is present in the graphite substrate ≧ 50 μ ι η below the outer surface of the graphite substrate.
12. The process chamber component of claim 10, having modified pores and unmodified pores, the modified pores having a diameter two to eight times the diameter of the unmodified pores.
13. The process chamber component of claim 10, wherein the graphite substrate has an average grain size of 0.015mm to 0.04 mm.
14. The process chamber component of claim 10, wherein the graphite substrate has a density of 1.50g/cm 3 To 1.75g/cm 3 The density of (c).
15. The process chamber component of claim 10, wherein the graphite substrate comprises an amount of one or more of the following elements:
less than 50.00ppb by weight of calcium,
less than 50.00ppb by weight of magnesium,
less than 50.00ppb by weight of aluminium,
less than 10.00ppb by weight of titanium,
less than 100.00ppb by weight of chromium,
less than 10.00ppb by weight of manganese,
less than 50.00ppb by weight of copper,
(ii) less than 10.00ppb by weight of iron,
less than 10.00ppb by weight of cobalt,
(ii) less than 10.00ppb by weight of nickel,
< 50.00ppb by weight of zinc, or
Less than 150.00ppb by weight of molybdenum.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210913459.5A CN115353415A (en) | 2017-12-27 | 2018-12-22 | Process for manufacturing a silicon carbide coated body |
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| Application Number | Priority Date | Filing Date | Title |
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| US201762610695P | 2017-12-27 | 2017-12-27 | |
| US62/610,695 | 2017-12-27 | ||
| EP18152230.1 | 2018-01-18 | ||
| EP18152230.1A EP3514257A1 (en) | 2018-01-18 | 2018-01-18 | Process for manufacturing a silicon carbide coated body |
| PCT/US2018/067418 WO2019133559A1 (en) | 2017-12-27 | 2018-12-22 | Process for manufacturing a silicon carbide coated body |
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| CN202210913459.5A Division CN115353415A (en) | 2017-12-27 | 2018-12-22 | Process for manufacturing a silicon carbide coated body |
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| CN111788168B true CN111788168B (en) | 2022-08-16 |
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| CN201880090409.3A Active CN111788168B (en) | 2017-12-27 | 2018-12-22 | Process for manufacturing a silicon carbide coated body |
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| US (1) | US20210062336A1 (en) |
| EP (2) | EP3514257A1 (en) |
| JP (1) | JP7004822B2 (en) |
| KR (2) | KR102593565B1 (en) |
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| WO (1) | WO2019133559A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021007319A1 (en) * | 2019-07-09 | 2021-01-14 | Entegris, Inc. | Porous carbonaceous vacuum chamber liners |
| US11827999B2 (en) | 2021-01-12 | 2023-11-28 | Applied Materials, Inc. | Methods of forming silicon carbide coated base substrates at multiple temperatures |
| CN117248275A (en) * | 2023-11-20 | 2023-12-19 | 希科半导体科技(苏州)有限公司 | Silicon carbide chemical vapor deposition epitaxial method and silicon carbide epitaxial wafer |
Family Cites Families (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2914328A (en) | 1958-06-04 | 1959-11-24 | Professional Golf Company | Steel power-center golf ball |
| GB1021662A (en) | 1962-03-27 | 1966-03-09 | Morganite Res & Dev Ltd | Treatment of porous bodies |
| US3406044A (en) | 1965-01-04 | 1968-10-15 | Monsanto Co | Resistance heating elements and method of conditioning the heating surfaces thereof |
| GB1128757A (en) | 1966-05-05 | 1968-10-02 | Texas Instruments Inc | Vapor deposition process for producing ªß-silicon carbide |
| US3622369A (en) | 1967-02-24 | 1971-11-23 | United Aircraft Corp | Process for forming stoichiometric silicon carbide coatings and filaments |
| US3925577A (en) * | 1972-11-24 | 1975-12-09 | Westinghouse Electric Corp | Silicon carbide coated graphite members and process for producing the same |
| US5045398A (en) * | 1982-06-22 | 1991-09-03 | Harry Levin | Silicon carbide product |
| EP0121797B1 (en) | 1983-03-15 | 1990-01-17 | Refractory Composites Inc. | Carbon composite article and method of making same |
| JPS6355182A (en) * | 1986-08-26 | 1988-03-09 | 電気化学工業株式会社 | Glassy carbon coated body |
| FR2611198B1 (en) | 1987-02-25 | 1991-12-06 | Aerospatiale | COMPOSITE MATERIAL WITH MATRIX AND CARBON REINFORCING FIBERS AND METHOD FOR MANUFACTURING THE SAME |
| NO881270L (en) | 1987-05-14 | 1988-11-15 | Dow Corning | PROCEDURE FOR AA REDUCING CARBON CONTENT IN SEMI-CONDUCTORS. |
| US4892788A (en) | 1988-03-28 | 1990-01-09 | Air Products And Chemicals, Inc. | Graphite brazing fixture coated with composite layers of titanium carbide and titanium nitride |
| JPH0825825B2 (en) * | 1990-03-05 | 1996-03-13 | 東芝セラミックス株式会社 | Silicon carbide coated graphite product and manufacturing method thereof |
| CA2163221C (en) | 1993-05-21 | 2001-10-30 | Stratmin Inc. | Process and apparatus for the purification of graphite |
| US5677082A (en) * | 1996-05-29 | 1997-10-14 | Ucar Carbon Technology Corporation | Compacted carbon for electrochemical cells |
| JPH1017382A (en) * | 1996-06-28 | 1998-01-20 | Mitsubishi Pencil Co Ltd | Production of silicon carbide formed body |
| JP3958397B2 (en) * | 1997-02-17 | 2007-08-15 | 東洋炭素株式会社 | Method for producing chemical vapor deposition silicon carbide material |
| JPH10236893A (en) * | 1997-02-24 | 1998-09-08 | Sumitomo Metal Ind Ltd | Carbon material coated with silicon carbide |
| JPH1179846A (en) * | 1997-09-01 | 1999-03-23 | Tokai Carbon Co Ltd | Silicon carbide formed product |
| EP1253123B1 (en) * | 1997-09-05 | 2014-04-16 | Element Six Limited | A diamond-silicon carbide-silicon composite |
| JP3773341B2 (en) * | 1997-10-31 | 2006-05-10 | 東海カーボン株式会社 | SiC coated carbon material |
| JP4043003B2 (en) | 1998-02-09 | 2008-02-06 | 東海カーボン株式会社 | SiC molded body and manufacturing method thereof |
| JP2000302577A (en) * | 1999-04-22 | 2000-10-31 | Tokai Carbon Co Ltd | Graphite member coated with silicon carbide |
| JP2000302576A (en) | 1999-04-22 | 2000-10-31 | Tokai Carbon Co Ltd | Graphite material coated with silicon carbide |
| JP2001048649A (en) | 1999-07-30 | 2001-02-20 | Asahi Glass Co Ltd | Silicon carbide and its production |
| JP4071919B2 (en) * | 2000-06-20 | 2008-04-02 | 東海カーボン株式会社 | SiC-coated graphite member and method for producing the same |
| US6881680B2 (en) | 2002-06-14 | 2005-04-19 | Toyo Tanso Co., Ltd. | Low nitrogen concentration carbonaceous material and manufacturing method thereof |
| US6881262B1 (en) * | 2002-12-23 | 2005-04-19 | Saint-Gobain Ceramics & Plastics, Inc. | Methods for forming high purity components and components formed thereby |
| JP3764157B2 (en) | 2003-10-10 | 2006-04-05 | 東洋炭素株式会社 | High-purity carbon-based material and ceramic film-coated high-purity carbon-based material |
| FR2889087B1 (en) * | 2005-07-28 | 2008-09-12 | Saint Gobain Ct Recherches | COOKING SUPPORT FOR CERAMICS AND METHOD OF OBTAINING |
| WO2009107884A1 (en) * | 2008-02-28 | 2009-09-03 | Changwon National University Industry Academy Cooperation Corps | Synthetic method for anti-oxidation ceramic coatings on graphite substrates |
| FR2935636B1 (en) | 2008-09-05 | 2011-06-24 | Commissariat Energie Atomique | MATERIAL WITH MULTILAYER ARCHITECTURE, DEDICATED TO CONTACT WITH LIQUID SILICON |
| EP2834192B1 (en) * | 2012-04-05 | 2018-01-03 | Imerys Graphite & Carbon Switzerland Ltd. | Surface-oxidized low surface area graphite, processes for making it, and applications of the same |
| CN102850087B (en) * | 2012-09-29 | 2014-10-29 | 西安超码科技有限公司 | Method for preparing silicon carbide coating on graphite surface |
| TWI500806B (en) | 2014-03-10 | 2015-09-21 | Nat Univ Tsing Hua | Method for manufacturing silicon carbide thin film |
| US10753010B2 (en) * | 2014-09-25 | 2020-08-25 | Pallidus, Inc. | Vapor deposition apparatus and techniques using high puritiy polymer derived silicon carbide |
| WO2016121642A1 (en) * | 2015-01-29 | 2016-08-04 | イビデン株式会社 | Sic-coated carbon composite material |
| TWI711072B (en) * | 2015-07-31 | 2020-11-21 | 挪威商卡亞奈米公司 | Processes for growing nanowires or nanopyramids |
| EP3338306A4 (en) * | 2015-08-20 | 2019-05-01 | Entegris, Inc. | Silicon carbide/graphite composite and articles and assemblies comprising same |
| CN105503270B (en) * | 2015-12-17 | 2018-05-22 | 湖南博望碳陶有限公司 | A kind of preparation method of SiC coatings |
| EP3514127A1 (en) * | 2018-01-18 | 2019-07-24 | Heraeus GMSI LLC | Process for manufacturing a silicon carbide coated body |
-
2018
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- 2018-12-22 CN CN202210913459.5A patent/CN115353415A/en active Pending
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| KR102480454B1 (en) | 2022-12-30 |
| EP3514257A1 (en) | 2019-07-24 |
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| CN111788168A (en) | 2020-10-16 |
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| CN115353415A (en) | 2022-11-18 |
| KR20200104370A (en) | 2020-09-03 |
| US20210062336A1 (en) | 2021-03-04 |
| KR102593565B1 (en) | 2023-10-26 |
| EP3732157A1 (en) | 2020-11-04 |
| JP2021508659A (en) | 2021-03-11 |
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